CN118284642A - Method of making recyclable copolyester articles with living hinges - Google Patents

Abstract

A method of making a recyclable, reclosable lid with a living hinge made from a copolyester composition comprising terephthalic acid residues, 1,4-cyclohexanedimethanol (CHDM) residues, and ethylene glycol (EG) residues within a specific composition range, which has low haze and is recyclable in a PET stream.

Description

Method for making recyclable copolyester articles having living hinges

Field of the Invention

The present disclosure relates to a method of making a recyclable, reclosable lid with a living hinge made from a copolyester composition comprising terephthalic acid residues, 1,4-cyclohexanedimethanol (CHDM) residues, and ethylene glycol (EG) residues within a specific composition range having certain advantages and improved properties.

The present disclosure further relates to a method of making a fully recyclable packaging article comprising (1) a reclosable lid with a living hinge comprising a RIC1-compatible copolyester composition, (2) a container comprising a RIC1-compatible copolyester composition; and attached thereto (3) a crystallizable shrinkable film or label comprising a copolyester composition recyclable in a PET stream.

Background of the Invention

There is a commercial need for fully recyclable containers and packaging articles, wherein the individual components of the article, ie, the cap, container and label, are recyclable in the PET stream.

To be considered recyclable, an article must be convertible back into a useful polymer material at the end of its life. Currently, poly(ethylene terephthalate) (PET) is the largest volume thermoplastic with an existing and well-established mechanical recycling stream.

The recycling of post-consumer PET is a complex process that involves separating opaque, colored, and transparent components from each other and from containers made of different materials (e.g., polyethylene, polypropylene, PVC, etc.). Proper separation is critical because each of these materials can contaminate the PET stream and reduce the quality of the final sorted product. After separation, the transparent PET bottles are ground into chips, cleaned, and dried at a temperature of 140° C. to 180° C. The chips can be used directly (e.g., in strapping and fiber extrusion) or further processed into pellets for film, sheet, or bottle applications. For some applications, the pellets can be further crystallized and solid-state polymerized at a temperature of 200° C. to 220° C. before use. Due to the well-established nature of the PET recycling process, it is desirable that copolyester-based molded articles and containers are compatible with existing PET recycling streams.

In the past, lids with living hinges were made from olefins such as polypropylene and polyethylene that are incompatible with the PET recycle stream.

The present disclosure addresses a long-standing commercial need for durable molded articles with living hinges made from copolyester thermoplastic materials that are transparent and clear, strong, flexible, and recyclable in the PET stream.

SUMMARY OF THE INVENTION

One aspect of the present invention is a method for producing a recyclable cap comprising injecting at least one molten polyester into a mold using one or more injection points to produce a reclosable cap having a living hinge, wherein the average polyester flow length divided by the average thickness of the cap is less than 200; wherein the at least one polyester comprises: (a) a dicarboxylic acid component comprising: i) 88 to 100 mole % of terephthalic acid residues; ii) 0 to 12 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: i) 0 to 12 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; ii) 0 to 12 mole % of 1,4-cyclohexanedimethanol residues; iii) 0 to 12 mole % of neopentyl glycol residues; iv) 0 to 12 mole % of DEG; v) 0 to 12 mole % of TMCD; vi ) 0 to 12 mol % MPDiol; vii) 0 to 12 mol % other modifying diol residues; viii) up to 100 mol % ethylene glycol residues; wherein the total mole % of the dicarboxylic acid component is 100 mol % and the total mole % of the diol component is 100 mol %; and wherein the polyester has a total comonomer content of 0-12 wt % from diols and acids other than ethylene glycol (EG), terephthalic acid (TPA) or dimethyl terephthalate (DMT) or any combination thereof, which must be less than 12 wt %; wherein the polyester has an intrinsic viscosity of 0.60 to 1.1 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; wherein the polyester has a Tg of 70 to 115°C; wherein the cap has a melting temperature ( _Tm ) of 225-255°C.

One aspect of the present disclosure is a method of producing a recyclable cap comprising injecting at least one molten polyester into a mold using one or more injection points to produce a reclosable cap having a living hinge, wherein the average polyester flow length divided by the average thickness of the cap is less than 200; wherein the at least one polyester comprises: (a) a dicarboxylic acid component comprising: (i) 88 to 100 mole % of terephthalic acid residues; (ii) 0 to 12 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) ) a diol component comprising: (i) 88 to 100 mole % of ethylene glycol residues; and (ii) 0 to 12 mole % of 1,4-cyclohexanedimethanol residues; wherein the total mole % of acid residues is 100 mole % and the total mole % of diol residues is 100 mole %; wherein the polyester has an intrinsic viscosity (IhV) of 0.60 to 1.1 dL/g as measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25° C.; and wherein the polyester has a melting point temperature (T _m ) of 225 to 255° C. as measured by ASTM D3418 at a scan rate of 10° C./min.

One embodiment is the method of the preceding aspect, wherein the average polyester flow length divided by the average thickness of the cap is less than 175; or wherein the average polyester flow length divided by the average thickness of the cap is less than 150, or wherein the average polyester flow length divided by the average thickness of the cap is less than 100.

One embodiment is the method of the preceding aspect and embodiment, wherein the mold has one injection point. In another embodiment, the mold has two injection points.

One embodiment is the method of the preceding aspect and embodiment, wherein the cover is substantially transparent, transparent and/or clear.

One embodiment is the method of the preceding aspect and embodiment, wherein the cap is recyclable in a PET recycling stream.

One embodiment is the method of the preceding aspect and embodiment, wherein the cover has an average thickness of 0.5-2 mm.

One embodiment is the method of the preceding aspect and embodiment, wherein the living hinge has an average thickness of 0.1-1 mm.

One embodiment is the method of the preceding aspect and embodiment, wherein the width of the living hinge is 20-80% of the length of the lid.

One embodiment of the present disclosure is an injection molded reclosable lid having a living hinge.

In one aspect, the reclosable lids of the present disclosure are recyclable in a PET recycling stream.

In one embodiment, the reclosable lids of the present disclosure can be used for packaging containers and molded articles, including manufactured articles selected from at least one of the following: molded articles, packages, packaging systems, bottles, films, sheets, containers, medical containers, dental containers, dental floss containers, personal care containers, fragrance containers, gum and candy containers, food containers, storage containers, beverage containers, or cosmetic containers.

In one embodiment, the articles of the present disclosure may be used with reclosable lids for containers, packaging articles, cosmetic packaging, cosmetic jars, bottles, medical containers, personal care containers, molded articles, lids, fragrance caps, medical devices, medical packaging, healthcare supplies, commercial food service products, trays, containers, food trays or trays, tumblers, storage boxes, storage containers, or toys.

The present disclosure relates to polyester compositions and methods capable of producing molded articles, reclosable lids, and reclosable hinged containers with living hinges that exhibit improved strength while maintaining desired flexibility.

One aspect of the present disclosure relates to a living hinge or a living or flexible hinge. In one embodiment, the living hinge is a one-piece curved or functional hinge having a bending zone between the attachment edges. The hinge body has an attachment edge and a bending zone defining a bending axis or pivot between the attachment edges. In one embodiment, the lid is a reclosable hinged article. In one embodiment, the reclosable lid and the living hinge are a single article. One embodiment of the present disclosure is an injection molded reclosable lid with a living hinge. The lid in the present disclosure can be attached to the container by any means suitable for the intended application. For example, in one embodiment, the lid is attached by screwing onto the container. In another embodiment, the lid is snapped or clicked to lock onto the container. In one embodiment, the reclosable lid and the container are a single article. In one embodiment, the reclosable lid and/or the container are multilayered. The living hinge of the present disclosure has improved reliability, stability, strength and durability, which is compatible with or superior to conventional olefin living hinges in performance.

Details

The present disclosure is more easily understood with reference to the following detailed description of certain embodiments and examples of the present disclosure. According to the purpose of the present disclosure, certain embodiments of the present disclosure are described in the summary of the invention and further described below. Other embodiments of the present disclosure are also described herein.

The present disclosure relates to specific copolyester compositions that can be made into articles having the following attributes, all of which are becoming increasingly important to meet market demands: (1) the copolyester compositions are used to make reclosable lids with living hinges; (2) the various components of the article - lids, containers and films - are recyclable in PET recycling streams; (3) in some embodiments, the articles contain post-consumer recycled (PCR) material in the form of rPET or recycled copolyester, or the articles are made from polyesters containing recycled content such as rEG, rDMT, rDEG or rCHDM; (4) the articles are transparent (low haze); (5) the compositions have a melting temperature ( _Tm ) of 225-255°C, so they qualify as PET for recycling purposes and can be recycled at end of life with existing well-established PET recycling streams; and (6) the articles include shrink films made from crystallizable resins with high strain-induced crystallization melting points, so they are compatible in PET recycling processes, so they do not have to be removed during the recycling process, and they do not affect the process.

In one aspect, the molded articles of the present disclosure relate to environmentally friendly and sustainable copolyester-based articles for durable and consumer-oriented product applications having two key attributes. First, the articles of the present disclosure enable the ability to mold articles with transparent reclosable lids with active hinges. Second, the various components of the articles of the present disclosure (lid, container, and label) are compatible in the PET recycling stream, i.e., they can be processed under conditions used for homopolymer PET recycling.

In 2017, California Assembly Bill No. 906-Beverage containers: polyethylene terephthalate was signed into law, and it defines “polyethylene terephthalate” (PET) for the purpose of resin code labeling as a plastic that meets certain conditions, including restrictions on the chemical composition of the polymer and a melting peak temperature within a specified range. AB-906 adds Section 18013 to California’s Public Resources Code, which reads in part: “Polyethylene terephthalate (PET)” means a plastic derived from the reaction between terephthalic acid or dimethyl terephthalate and monoethylene glycol, which meets the following two conditions:

a. The reacted terephthalic acid or dimethyl terephthalate and monoethylene glycol constitute at least 90% by mass of the monomers reacted to form the polymer.

b. The plastic exhibits a melting peak temperature between 225°C and 255°C as determined during the second thermal scan using Procedure 10.1 set forth in ASTM International (ASTM) D3418 at a sample heating rate of 10°C/minute.

Therefore, the copolyesters of the present disclosure meet both of the conditions outlined in AB-906 and are acceptable for being called "PET", so such materials are likely to be compatible in the current PET recycling stream. In addition, the articles of the present disclosure meet the California (AB 906)/ASTM 7611 guidelines for the definition of RIC1, and they have been approved by the Association of Plastic Recyclers (APR) Critical Guidance.

The melting points of the copolyester compositions of the present disclosure make them acceptable as PET under this definition and therefore compatible in current PET recycling streams.

Thus, in one aspect of the present disclosure, "compatible with PET recycle streams" is defined as exhibiting a melt temperature of 225-255°C in the first heating DSC scan of the molded article (at a scan rate of 10-20°C/min) while also containing 15 wt% or less of diols and/or acids other than EG, TPA or DMT (referred to herein as the total wt% of comonomer content).

The molded articles of the present disclosure are also recyclable, and they can be processed with the PET recycling stream and eventually become a component in the recyclable PET bottle flakes leaving the recycling process. Therefore, they exhibit good properties as molded articles, and they have a high melting point, so they provide excellent performance in the recycling process. The molded articles of the present disclosure have a melting temperature and a weight % comonomer content loading that are consistent with the definition in the Assembly Bill, so it is expected that the molded articles of the present disclosure can be processed in a standard PET recycling process, and they do not have to be removed during the recycling process because they do not affect the process.

In one aspect of the present disclosure, the presence of a melting temperature peak is critical to functional adoption as a recyclable PET material.The articles of the present disclosure exhibit a melting temperature of 225-255°C and have a total comonomer content of 0-15 wt%.

In one embodiment, the article has a melting temperature ( _Tm ) of 225-255°C. In one embodiment, the article has a melting temperature ( _Tm ) of 230-250°C. In another embodiment, the article has a melting temperature ( _Tm ) of 235-245°C. In another embodiment, the article has a melting temperature ( _Tm ) of 230-240°C.

The term "polyester" as used herein is intended to include "copolyesters" and is understood to refer to a synthetic polymer made by the reaction of one or more difunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or polyfunctional hydroxyl compounds, such as branching agents. Typically, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxyl compound can be a dihydric alcohol, such as glycols and diols. The term "glycol" as used herein includes, but is not limited to, diols, glycols and/or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid can be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound can have an aromatic core with 2 hydroxyl substituents, such as hydroquinone. The term "residue" as used herein refers to any organic structure incorporated into a polymer from the corresponding monomer by polycondensation and/or esterification reactions. The term "repeat unit" as used herein refers to an organic structure having a dicarboxylic acid residue and a diol residue bonded via an ester group. Thus, for example, a dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acyl halides, esters, salts, anhydrides and/or mixtures thereof. In addition, the term "diacid" as used herein includes polyfunctional acids, such as branching agents. Thus, the term "dicarboxylic acid" as used herein is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids that can be used in the process of reacting with a diol to make a polyester, including its associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides and/or mixtures thereof. The term "terephthalic acid" as used herein is intended to include terephthalic acid itself and its residues that can be used in the process of reacting with a diol to make a polyester, as well as any derivatives of terephthalic acid, including its associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides and/or mixtures thereof or residues thereof.

The polyesters used in the present disclosure can generally be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters of the present disclosure may therefore contain substantially equal molar proportions of acid residues (100 mole %) and diol (and/or polyfunctional hydroxy compound) residues (100 mole %) to make the total mole number of repeating units equal to 100 mole %. Therefore, the mole percentages provided in the present disclosure may be based on the total mole number of acid residues, the total mole number of diol residues, or the total mole number of repeating units. For example, a polyester containing 10 mole % of isophthalic acid based on the total acid residues means that the polyester contains 10 mole % of isophthalic acid residues in a total of 100 mole % of acid residues. Therefore, there are 10 moles of isophthalic acid residues in every 100 moles of acid residues. In another example, a polyester containing 25 mole % of 1,4-cyclohexanedimethanol based on the total diol residues means that the polyester contains 25 mole % of 1,4-cyclohexanedimethanol residues in a total of 100 mole % of diol residues. Thus, there are 25 moles of 1,4-cyclohexanedimethanol residues for every 100 moles of diol residues.

In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or a mixture of terephthalic acid residues and their esters may constitute part or all of the dicarboxylic acid component used to form a polyester that can be used in the present disclosure. In certain embodiments, terephthalic acid residues may constitute part or all of the dicarboxylic acid component used to form a polyester that can be used in the present disclosure. For the purposes of the present disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate (DMT) is part or all of the dicarboxylic acid component used to make a polyester that can be used in the present disclosure. In an embodiment, 70 to 100 mol%; or 80 to 100 mol%; or 90 to 100 mol%; or a range of 99 to 100 mol%; or 100 mol% of terephthalic acid and/or dimethyl terephthalate and/or a mixture thereof may be used. In one embodiment, DMT is rDMT.

In addition to terephthalic acid, the dicarboxylic acid component that can be used for the polyester of the present disclosure can also include up to 30 mol %, up to 20 mol %, up to 10 mol %, up to 5 mol % or up to 1 mol % of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mol % modified aromatic dicarboxylic acid. Therefore, if present, it is estimated that the amount of one or more modified aromatic dicarboxylic acids can start from any of these aforementioned endpoints, including, for example, 0.01 to 30 mol %, 0.01 to 20 mol %, 0.01 to 10 mol %, 0.01 to 5 mol % and 0.01 to 1 mol %. In one embodiment, the modified aromatic dicarboxylic acids that can be used for the present disclosure include, but are not limited to, those having up to 20 carbon atoms, which can be linear, para-oriented or symmetrical. Examples of modified aromatic dicarboxylic acids useful in the present disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalene dicarboxylic acid, and trans-4,4'-stilbene dicarboxylic acid, and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

The carboxylic acid component of the polyester useful in the present disclosure may be further modified with up to 15 mol%, up to 12 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more aliphatic dicarboxylic acids containing 2 to 20 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dodecanedicarboxylic acid. Certain embodiments may also contain 0 to 15 mol%, 0.01 to 15 mol%, 0 to 12 mol%, 0.01 to 12 mol%, 0 to 10 mol%, 0.01 to 10 mol%, such as 0.1 to 15 mol%, 1 to 15 mol%, 5 to 15 mol%, or 0.1 to 12 mol%, 1 to 12 mol%, 5 to 12 mol%, or 0.1 to 10 mol%, 1 or 10 mol%, 5 to 10 mol% of one or more modified aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole % of the modified aliphatic dicarboxylic acid. The total mole % of the dicarboxylic acid component is 100 mole %. In one embodiment, adipic acid and/or glutaric acid are provided in the modified aliphatic dicarboxylic acid component of the polyester and can be used in the present disclosure.

Can use terephthalic acid ester and other modified dicarboxylic acid or their corresponding ester and/or salt to replace dicarboxylic acid.Suitable example of dicarboxylic acid ester includes but not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester.In one embodiment, this ester is selected from following at least one: methyl ester, ethyl ester, propyl ester, isopropyl ester and phenyl ester.

In one embodiment, at least a portion of the residues of dicarboxylic acids and diols as described herein are derived from recycled monomer species, such as recycled dimethyl terephthalate (rDMT), recycled terephthalic acid (rTPA), recycled dimethyl isophthalate (rDMI), recycled ethylene glycol (rEG), recycled cyclohexanedimethanol (rCHDM), recycled neopentyl glycol (rNPG), and recycled diethylene glycol (rDEG). Such recycled monomer species can be obtained from known methanolysis or glycolysis reactions for depolymerizing various post-consumer recycled polyesters and copolyesters. Similarly, recycled poly(ethylene terephthalate) (rPET) can be used as a raw material (for dicarboxylic acid and diol residues) in the manufacture of polyesters with recycled material content of the present disclosure. Therefore, in another embodiment, the polyester composition of the present disclosure comprises at least a portion of dicarboxylic acid residues and/or diol residues derived from (i) recycled monomer species selected from rDMT, rTPA, rDMI, rEG, rCHDM, rDEG, rNPG and (ii) rPET.

In some embodiments, the composition can be used as a polyester reactant or intermediate in a reaction scheme to provide a copolyester product containing recycle content. In these embodiments, the recycle content composition obtains its recycle content from r-propylene, which in turn obtains its recycle content from r-pyoil. In these embodiments, such a recycle content composition can be selected from r-isobutyraldehyde, r-isobutyric acid, r-isobutyric anhydride, r-dimethyl ketene, rTMCDn or r-TMCD.

In one embodiment, the diol component useful for the copolyester composition of the present disclosure may include 1,4-cyclohexanedimethanol. In another embodiment, the diol component useful for the copolyester composition of the present disclosure includes 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis/trans 1,4-cyclohexanedimethanol may range from 50/50 to 0/100, for example, from 40/60 to 20/80.

In one embodiment, the diol component useful for the copolyester composition of the present disclosure may include 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In another embodiment, the molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be different for each pure form and mixtures thereof. In certain embodiments, the molar percentage of cis and/or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans; or greater than 55 mol% cis and less than 45 mol% trans; or 50 to 70 mol% cis and 50 to 30 mol% trans; or 60 to 70 mol% cis and 30 to 40 mol% trans; or greater than 70 mol% cis and less than 30 mol% trans; wherein the total molar percentage of cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mol%. In additional embodiments, the molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may range from 50/50 to 0/100, such as from 40/60 to 20/80.

In one embodiment, the total comonomer content from diols and acids other than ethylene glycol (EG), terephthalic acid (TPA) or dimethyl terephthalate (DMT) useful in the copolyester compositions of the present disclosure is 0 to 15 wt%, 0 to 14 wt%, 0 to 12 wt%, 0 to 11 wt%, 0 to 10 wt%, 0 to 8 wt%, 0 to 6 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to 2 wt%, 1 to 15 wt%, 1 to 14 wt%, 1 to 12 wt%, 1 to 11 wt%, 1 to 10 wt%, 1 to 8 wt%, 1 to 6 wt%, 1 to 5 wt%, 1 to 4 wt%, 1 to 4.5 wt%, 1 to 3.5 wt%, 1 to 2 wt%. %, 2 to 12 wt %, or 5 to 10 wt %, or 10 to 15 wt %, or 2 to 15 wt %, or 2 to 10 wt %, or 3 to 15 wt %, or 3 to 10 wt %, or 4 to 15 wt %, or 4 to 12 wt %, 4 to 11 wt %, 4 to 10 wt %, 5 to 12 wt %, 6 to 12 wt %, 2 to 8 wt %, 2 to 12 wt %, or 3 to 12 wt %, or 6 to 10 wt %, or 7 to 15 wt %, or 7 to 10 wt %, or 8 to 15 wt %, or 8 to 10 wt %, or 9 to 15 wt %, or 9 to 10 wt %, or 11 to 15 wt %, 12 to 15 wt %, or 13 to 15 wt %, 14 to 15 wt %, or 12 to 15 wt %.

In one embodiment, the diol component that can be used for the copolyester composition of the present disclosure may contain 0 to 15 mol% of neopentyl glycol based on the total mole % of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the copolyester composition of the present disclosure may contain 0 to 14 mol% of neopentyl glycol based on the total mole % of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the copolyester composition of the present disclosure may contain 0 to 12 mol% of neopentyl glycol based on the total mole % of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the copolyester composition of the present disclosure may contain 0.1 to 15 mol% of neopentyl glycol based on the total mole % of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the copolyester composition of the present disclosure may contain 0.1 to 12 mol% of neopentyl glycol based on the total mole % of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 1 to 12 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 2 to 12 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 2 to 10 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%.

In one embodiment, the diol component useful in the copolyester composition of the present disclosure may contain 0 to 15 mol%, or 0 to 14 mol%, or 0 to 13 mol%, or 0 to 12 mol%, or 0 to 10 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 ...0 mol%. 9 mol%, or 0.01 to 8 mol%, or 0.01 to 9 mol%, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 0.01 to 4.5 mol%, or 0.01 to 4 mol%, or 0.01 to 3.5 mol%, or 0.01 to 3 mol%, or 0.01 to 2 mol%, or 0.1 to 15 mol%, or 0.1 to 14 mol%, or 0.1 to 13 mol%, or 0.1 to 12 mol%, or 0.1 to 10 mol%. %, or 0.1 to 8 mol%, 0.1 to 6 mol%, or 0.1 to 5 mol%, or 0.1 to 4 mol%, or 0.1 to 3 mol%, or 0.1 to 2 mol%, or 0.1 to 4.5 mol%, or 0.1 to 3.5 mol%, 3.5 to 4.5 mol%, or 10 to 12 mol%, or 10 to 15 mol%, or 2 to 15 mol%, or 2 to 14 mol%, or 2 to 13 mol%, or 2 to 12 mol%, 3 to 15 mol%, or 3 to 14 mol%, or 3 %, or 3 to 12 mol %, or 3 to 11 mol %, or 3 to 10 mol %, or 3 to 9 mol %, or 3 to 8 mol %, or 3 to 7 mol %, or 2 to 15 mol %, or 2 to 12 mol %, or 2 to 10 mol %, or 2 to 9 mol %, or 2 to 8 mol %, or 2 to 7 mol %, or 2 to 5 mol %, or 2 to 4 mol %, or 1 to 7 mol %, or 1 to 6 mol %, or 1 to 5 mol %, or 1 to 4 mol %, or 1 to 3 mol % neopentyl glycol residues.

In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to 15 mol% of 2-methyl-1,3-propanediol (MPDiol), based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to 15 mol%, or 0 to 14 mol%, or 0 to 13 mol%, or 0 to 12 mol%, or 0 to 10 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 1 0 mol%, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 0.01 to 4 mol%, or 0.01 to 3 mol%, or 0.01 to 2 mol%, or 0.1 to 15 mol%, or 0.1 to 14 mol%, or 0.1 to 13 mol%, or 0.1 to 12 mol%, or 0.1 to 11 mol%, or 0.1 to 10 mol%, or 5 % or 2 to 15 mol%, 10 to 12 mol%, or 9 to 11 mol%, or 8 to 12 mol%, or 6 to 12 mol%, or 3 to 12 mol%, or 4 to 12 mol%, or 3 to 11 mol%, 4 to 11 mol%, or 3 to 10 mol%, or 4 to 10 mol%, or 2 to 14 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 4 mol%, or 2 to 6 mol%, or 3 to 15 mol%, or 3 to 14 mol%, or 3 to 13 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 5 mol%, or 2 to 4.5 mol%, or 1 to 7 mol%, or 1 to 5 mol%, or 1 to 4 mol% of 2-methyl-1,3-propanediol residues.

In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to 12 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0.01 to less than 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0.01 to 12 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0.01 to less than 12 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to less than 5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4.5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 3.5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component useful in the copolyester composition of the present disclosure may contain 3 mole % of 1,4-cyclohexanedimethanol based on the total mole % of the diol component being 100 mole %.

In one embodiment, 1,4-cyclohexanedimethanol (CHDM) is rCHDM. In one embodiment, rCHDM is made from rDMT.

In one embodiment, the diol component useful in the copolyester composition of the present disclosure may contain 0 to 15 mol%, or 0 to 14 mol%, or 0 to 13 mol%, or 0 to 12 mol%, or 0 to 10 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 1 0 mol%, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 0.01 to 4 mol%, or 0.01 to 3 mol%, or 0.01 to 2 mol%, or 0.1 to 15 mol%, or 0.1 to 14 mol%, or 0.1 to 13 mol%, or 0.1 to 12 mol%, or 0.1 to 11 mol%, or 0.1 to 10 mol%, or 5 to 15 mol%, 10 to 12 mol%, or 9 to 11 mol%, or 8 to 12 mol%, or 6 to 12 mol%, or 3 to 12 mol%, or 4 to 12 mol%, or 3 to 11 mol%, 4 to 11 mol%, or 3 to 10 mol%, or 4 to 10 mol%, or 2 to 14 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 4 mol%, or 2 to 6 mol%, or 3 to 15 mol%, or 3 to 14 mol%, or 3 to % or 1 to 4 mol % of 1,4-cyclohexanedimethanol residues.

In one embodiment, the diol component useful in the copolyester composition of the present disclosure may contain, based on the total mole % of the diol component being 100 mole %, 0 to 15 mole %, or 0 to 14 mole %, or 0 to 13 mole %, or 0 to 12 mole %, or 0 to 11 mole %, or 0 to 10 mole %, or 0 to 9 mole %, or 0 to 8 mole %, or 0 to 7 mole %, or 0 to 6 mole %, or 0 to 5 mole %, or 0 to 4.5 mole %, or 0 to 4 mole %, or 0 to 3.5 mole %, or 0 to 3 mole %, or 0 to 2 mole %, or 0.01 to 15 mole %, or 0.01 to 14 mole %, or 0.01 to 13 mole %, or 0.01 to 12 mole %, or 0.01 to 11 mole %, or 0.01 to 10 mole %, or 0.01 to 9 mole %, or 0.01 to 8 mole %, or 0.1 to 7 mole %. %, or 0.1 to 6 mol%, or 0.1 to 5 mol%, or 0.1 to 4.5 mol%, or 0.1 to 4 mol%, or 0.1 to 3.5 mol%, or 0.1 to 3 mol%, or 0.1 to 2 mol%, or 1 to 12 mol%, 2 to 12 mol%, or 1 to 10 mol%, or 2 to 10 mol%, 1 to 8 mol%, or 2 to 8 mol%, 3 to 15 mol%, or 3 to 14 mol%, or 3 to % or 1 to 3 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0 to 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 0.01 to less than 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 1 to 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 2 to less than 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 3 to 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4 to less than 12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4.5 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 3 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used in the copolyester composition of the present disclosure may contain 4.5 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol based on the total mol% of the diol component being 100 mol%.

It should be understood that some other diol residues may be formed in situ during processing. For example, in one embodiment, the total amount of diethylene glycol residues may be present in the copolyesters useful for the present disclosure, whether formed in situ during processing or intentionally added, or both, in any amount of, for example, 0 to 15 mol%, 0 to 12 mol%, 1 to 15 mol%, 1 to 12 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 4 to 12 mol%, or 4 to 11 mol%, or 4 to 10 mol%, or 4 to 9 mol%, or 5 to 12 mol%, or 5 to 11 mol%, or 5 to 10 mol%, or 5 to 9 mol% of diethylene glycol residues, based on the total mol% of the diol component being 100 mol%.

In one embodiment, the total amount of diethylene glycol (DEG) residues present in the copolyesters useful in the present disclosure, whether formed in situ during processing or intentionally added, or both, can be 12 mol % or less, or 10 mol % or less, or 8 mol % or less, or 6 mol % or less, or 5 mol % or less, or 4 mol % or less, or 3.5 mol % or less, or 3.0 mol % or less, or 2.5 mol % or less, or 2.0 mol % or less, or 1.5 mol % or less, based on the total mol % of the diol component being 100 mol %. In some embodiments, the copolyesters contain 1 to 2 mole % or less, or 1.0 mole % or less, or 0 to 12 mole %, or 1 to 12 mole %, or 1 to 10 mole %, or 1 to 8 mole %, or 1 to 6 mole %, or 1 to 5 mole %, or 1 to 4 mole %, or 1 to 3 mole %, or 1 to 2 mole % of diethylene glycol residues, or 2 to 8 mole %, or 2 to 7 mole %, or 2 to 6 mole %, or 2 to 5 mole %, or 3 to 8 mole %, or 3 to 7 mole %, or 3 to 6 mole %, or 3 to 5 mole %, or in some embodiments, there is no intentional addition of diethylene glycol residues. In certain embodiments, the copolyesters do not contain added modifying glycols. In certain embodiments, the diethylene glycol residues in the copolyesters can be 5 mole % or less. It should be noted that any low amount of DEG formed in situ is not included in the total polymonomer content from diols and acids other than EG, TPA or DMT.

In one embodiment, the DEG is rDEG. In one embodiment, the rDEG is made from rEG.

For all embodiments, the remaining diol component may contain any amount of ethylene glycol residues based on the total mole % of the diol component being 100 mole %. In one embodiment, the copolyesters useful in the present disclosure may contain 50 mole % or more, or 55 mole % or more, or 60 mole % or more, or 65 mole % or more, or 70 mole % or more, or 75 mole % or more, or 80 mole % or more, or 85 mole % or more, or 90 mole % or more, or 95 mole % or more, or 98 mole % or more, or 99 mole % or more; or 88 to 99 mole %, 80 to 99 mole %, 50 to 99 mole %, or 55 to 90 mole %, or 50 to 80 mole %, or 55 to 80 mole %, or 60 to 80 mole %, or 50 to 75 mole %, or 55 to 75 mole %, or 60 to 75 mole %, or 65 to 75 mole % of ethylene glycol residues based on the total mole % of the diol component being 100 mole %. In one embodiment, the diol component may comprise 100 mole % ethylene glycol residues.

In one embodiment, the ethylene glycol is rEG.

In one embodiment, the diol component useful in the copolyester compositions of the present disclosure may contain up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4.5 mol%, or up to 4 mol%, or up to 3.5 mol%, or up to 5 mol%. At most 3 mol%, or at most 2.5 mol%, or at most 2 mol%, or at most 1.5 mol%, or at most 1 mol%, or at most 0.5 mol%, or at most 0.1 mol% or less of one or more other modifying glycols (other modifying glycols are defined as glycols that are not ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol). In certain embodiments, the copolyesters useful in the present disclosure may contain 15 mol% or less of one or more other modifying glycols; 12 mol% or less of one or more other modifying glycols; 10 mol% or less of one or more other modifying glycols; 8 mol% or less of one or more other modifying glycols; 5 mol% or less of one or more other modifying glycols; 4 mol% or less of one or more other modifying glycols, or 3 mol% or less of one or more other modifying glycols. In certain embodiments, the copolyesters useful in the present disclosure may contain 4.5 mol % or less of one or more other modifying glycols. In certain embodiments, the copolyesters useful in the present disclosure may contain 3.5 mol % or less of one or more other modifying glycols. In another embodiment, the copolyesters useful in the present disclosure may contain 0 mol % of other modifying glycols. However, it is expected that some other glycol residues may be formed in situ, so that the residual amounts formed in situ are also an embodiment of the present disclosure.

In an embodiment, if used, other modified glycols for the copolyester as defined herein contain 2 to 20 carbon atoms. Examples of other modified glycols include, but are not limited to, 1,2-propylene glycol, 1,3-propylene glycol, isosorbide, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, and mixtures thereof. In one embodiment, isosorbide is another modified glycol. In another embodiment, other modified glycols include, but are not limited to, at least one of 1,3-propylene glycol and 1,4-butylene glycol. In one embodiment, 1,3-propylene glycol and/or 1,4-butylene glycol may be excluded. If 1,4- or 1,3-butylene glycol is used, greater than 4 mol % or greater than 5 mol % may be provided in one embodiment. In one embodiment, at least one other modified glycol is 1,4-butylene glycol present in an amount of 0 to 12 mol %.

In some embodiments, the copolyester composition according to the present disclosure may contain 0 to 10 mol%, for example, 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol%, or 0.05 to 2.0 mol%, 0.05 to 1.5 mol%, 0.05 to 1.0 mol%, 0.05 to 0.8 mol%, 0.05 to 0.6 mol%, 0.1 to 2.0 mol%, 0.1 to 1.5 mol%, 0.05 to 1.0 mol%, 0.05 to 0.8 mol%, 0.05 to 0.6 mol%, based on the total mole percentage of diol or diacid residues, respectively. % of one or more branching monomers (also referred to herein as branching agents) residues having 3 or more carboxyl substituents, hydroxyl substituents, or combinations thereof. In certain embodiments, the branching monomers or branching agents may be added before and/or during and/or after the polymerization of the copolyester. In some embodiments, the copolyesters useful in the present disclosure may therefore be linear or branched.

Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branching monomer residues may contain 0.1 to 0.7 mole % of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid. The branching monomers may be added to the copolyester reaction mixture or blended with the copolyester as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176 (the disclosures of which are incorporated herein by reference for branching monomers) in the form of a concentrate.

In one embodiment, the branching monomers or branching agents that can be used to make the copolyesters formed in the present disclosure can be those that provide branching in the acid unit portion of the copolyester or in the diol unit portion, or it can be hybridized. In some embodiments, some examples of branching agents are polyfunctional acids, polyfunctional acid anhydrides, polyfunctional diols and acid/diol hybrids. Examples include tri- or tetracarboxylic acids and their corresponding anhydrides, such as trimesic acid, pyromellitic acid and its low-carbon alkyl esters, etc., and tetraols, such as pentaerythritol. Triols such as trimethylolpropane or dihydroxy carboxylic acids and hydroxy dicarboxylic acids and derivatives, such as dimethyl hydroxy terephthalate, etc. can also be used in the present disclosure. In one embodiment, trimellitic anhydride is a branching monomer or branching agent.

The copolyester compositions useful in the present disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides, including, for example, epoxidized novolac resins and phenoxy resins. In one embodiment, the chain extender has epoxide dependent groups. In one embodiment, the chain extender additive may be one or more styrene-acrylate copolymers having epoxy functionality. In one embodiment, the chain extender additive may be one or more copolymers of glycidyl methacrylate and styrene.

In certain embodiments, the chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extenders may be incorporated by compounding or by addition during a conversion process such as injection molding or extrusion. In certain embodiments, the chain extenders may be added to the rPET, to the copolyester, or to the blend during or after blending. In some embodiments, the chain extenders may be incorporated by compounding or by addition during a conversion process such as injection molding or extrusion.

The amount of chain extender used can vary depending on the specific monomer composition used and the desired physical properties, but is generally from about 0.05 wt % to about 10 wt %, such as from about 0.1 to about 10 wt %, or 0.1 to about 5 wt %, 0.1 to about 2 wt %, or 0.1 to about 1 wt %, based on the total weight of the copolyester composition. In one embodiment, the copolyester composition comprises 0.05 to 5 wt % of the chain extender, based on the total weight of the copolyester composition.

In some embodiments, chain extenders may also be added during melt processing to build molecular weight by "reactive extrusion" or "reactive chain coupling" or any other process known in the art.

In one embodiment, certain copolyester compositions useful in the present disclosure may exhibit a melt viscosity (MV) at a shear rate of 1 rad/sec of greater than 10,000 poise, or greater than 20,000 poise, or greater than 30,000 poise, or greater than 40,000 poise, or greater than 50,000 poise, or greater than 60,000 poise, or greater than 70,000 poise, or greater than 80,000 poise, or greater than 90,000 poise, or greater than 100,000 poise, wherein the melt viscosity is measured at 260° C. and 1 rad/sec using a rotational viscometer, such as a Rheometrics Dynamic Analyzer (RDAII). In one embodiment, certain copolyester compositions useful in the present disclosure may exhibit a melt viscosity (MV) at a shear rate of 1 rad/sec of 10,000 poise to 120,000 poise, or 20,000 poise to 80,000 poise, wherein the melt viscosity is measured using a rotational viscometer, such as a Rheometrics Dynamic Analyzer (RDA II) at 260° C. and 1 rad/sec.

Unless otherwise specified, it is contemplated that copolyester compositions useful in the present disclosure may have at least one intrinsic viscosity range described herein and at least one monomer range for copolyester compositions described herein. Unless otherwise specified, it is also contemplated that copolyester compositions useful in the present disclosure may have at least one Tg range described herein and at least one monomer range for copolyester compositions described herein. Unless otherwise specified, it is also contemplated that copolyester compositions useful in the present disclosure may have at least one intrinsic viscosity range described herein, at least one Tg range described herein, and at least one monomer range for copolyester compositions described herein.

For embodiments of the present disclosure, the copolyester compositions useful in the present disclosure may exhibit at least one of the following intrinsic viscosities measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25° C.: 0.50 to 1.2 dL/g; 0.50 to 1.0 dL/g; 0.50 to 0.90 dL/g; 0.50 to 0.80 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.0 dL/g; 0.55 to 0.90 dL/g; 0.55 to 0.80 dL/g; 0.58 to 1.2 dL/g; 0.58 to 1.0 dL/g /g; 0.58 to 0.90 dL/g; 0.58 to 0.80 dL/g; 0.60 to 1.1 dL/g; 0.60 to 0.90 dL/g; 0.60 to 0.80 dL/g; 0.65 to 0.90 dL/g; 0.60 to 0.80 dL/g; 0.70 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.55 to 0.75 dL/g; 0.58 to 0.75 dL/g; 0.60 to 0.75 dL/g; 0.60 to 0.70 dL/g; 0.58 to 0.70 dL/g; or 0.55 to 0.70 dL/g.

The glass transition temperature (Tg) of the copolyester composition was determined using a TA DSC 2920 from Thermal Analyst Instrument at a scanning rate of 20° C./min. The value of the glass transition temperature was determined during the second heating.

In certain embodiments, the molded articles of the present disclosure comprise a copolyester composition wherein the copolyester has a Tg of 65 to 120°C; 70 to 115°C; 70 to 80°C; 70 to 85°C; or 70 to 90°C; or 70 to 95°C; 70 to 100°C; 70 to 105°C; 70 to 110°C; 80 to 115°C; 80 to 85°C; or 80 to 90°C; or 80 to 95°C; 80 to 100°C; 80 to 105°C; 80 to 110°C; 90 to 115°C; 90 to 100°C; 90 to 105°C; 90 to 110°C.

In one embodiment, the copolyester compositions useful in the present disclosure are clear, substantially clear, or visually clear. The term "visually clear" is defined herein as the apparent absence of cloudiness, haziness, and/or muddiness upon visual inspection. In one embodiment, the copolyester blend compositions useful in the present disclosure are transparent. The term "transparent" is defined herein as the apparent absence of cloudiness, haziness, and/or muddiness, so that the material can be seen through upon visual inspection. These terms are used interchangeably herein. In one aspect, the terms clear and/or transparent are defined as having low haze. In one embodiment, clear and/or transparent are defined as having a haze value of 20% or less. In one embodiment, clear and/or transparent are defined as having a haze value of 15% or less. In one embodiment, clear and/or transparent are defined as having a haze value of 12% or less. In one embodiment, clear and/or transparent are defined as having a haze value of 10% or less. In one embodiment, clear and/or transparent are defined as having a haze value of 5% or less.

In some embodiments, the copolyester compositions in the present disclosure are fast crystallizing so that they are compatible with PET recycling streams. For example, in one embodiment, the copolyester composition has a half crystallization time of about 1 minute to about 20 minutes. For example, in another embodiment, the copolyester composition has a half crystallization time of about 3 minutes to about 20 minutes. In one embodiment, the copolyester composition has a half crystallization time of up to about 20 minutes, or up to about 15 minutes, or up to about 10 minutes, or up to about 5 minutes. In one embodiment, the copolyester composition is suitable for use as long as their half crystallization time is about 3 minutes. In another embodiment, the copolyester composition is suitable for use as long as their half crystallization time is about 5 minutes. In another embodiment, the copolyester composition is suitable for use as long as their half crystallization time is about 10 minutes. In another embodiment, the copolyester composition is suitable for use as long as their half crystallization time is about 15 minutes. In another embodiment, the copolyester composition is suitable for use as long as their half crystallization time is about 20 minutes. In another embodiment, the copolyester composition is suitable for use as long as their half crystallization time is less than about 20 minutes. In another embodiment, the copolyester compositions are suitable for use as long as their half crystallization time is less than about 15 minutes. In another embodiment, the copolyester compositions are suitable for use as long as their half crystallization time is less than about 10 minutes. In another embodiment, the copolyester compositions are suitable for use as long as their half crystallization time is less than about 5 minutes.

Conventional methods can be used to measure the half crystallization time of the copolyester composition as used herein. For example, in one embodiment, a differential scanning calorimeter (DSC) is used to measure the half crystallization time. In these cases, the sample is ramped up (20°C/min) to 285°C and kept isothermal for 2 minutes. Next, the polymer is rapidly dropped to the set point temperature (180°C) and maintained until crystallization is complete, as indicated by a completely endothermic heat flow curve. The half crystallization time is reported as the time from the start of crystallization to half the time of the peak formation.

In one embodiment, the copolyester composition can be produced by a process in a homogeneous solution, by a transesterification process in a melt, and by a two-phase interface process. Suitable methods include, but are not limited to, steps of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100° C. to 315° C. and a pressure of 0.1 to 760 mm Hg for a time sufficient to form a copolyester. For methods of producing copolyesters, see U.S. Pat. No. 3,772,405, which is incorporated herein by reference for its disclosure of such methods.

In one embodiment, the copolyesters may be made from chemically recycled monomers (made by any known depolymerization process).

In one aspect of the present disclosure, the copolyester composition comprises recycled content. In one embodiment, the copolyester composition is made from chemically recycled monomers. For example, the polyester is depolymerized to form the monomer units originally used for its manufacture. A commercially used polyester depolymerization process is methanolysis. In methanolysis, the polyester is reacted with methanol to produce a depolymerized polyester mixture comprising polyester oligomers, dimethyl terephthalate ("DMT") and ethylene glycol ("EG"). Other monomers, such as 1,4-cyclohexanedimethanol ("CHDM") and diethylene glycol may also be present, depending on the composition of the polyester in the methanolysis feed stream. Some representative processes for the methanolysis of PET are described in U.S. Pat. Nos. 3,037,050; 3,321,510; 3,776,945; 5,051,528; 5,298,530; 5,414,022; 5,432,203; 5,576,456 and 6,262,294, the contents and disclosures of which are incorporated herein by reference. A representative methanolysis process is also exemplified in U.S. Pat. No. 5,298,530, the contents and disclosures of which are incorporated herein by reference. The '530 patent describes a process for recovering ethylene glycol and dimethyl terephthalate from waste polyester. The process includes the steps of dissolving the waste polyester in ethylene glycol and oligomers of terephthalic acid or dimethyl terephthalate and passing superheated methanol through the mixture. The oligomers may comprise any low molecular weight polyester polymer having the same composition as the waste material used as the starting component, so that the waste polymer will dissolve in the low molecular weight oligomers. Dimethyl terephthalate and ethylene glycol are recovered from the methanol vapor stream exiting the depolymerization reactor.

Another method of depolymerizing polyesters is glycolization, in which the polyester is reacted with a glycol, such as ethylene glycol or CHDM, to produce a depolymerized polyester mixture. U.S. Pat. No. 4,259,478 thus discloses a method comprising heating a polyester in the presence of 1,4-cyclohexanedimethanol to glycolize the polymer, distilling off ethylene glycol from the glycolization mixture, and polycondensing the glycolization mixture to form a copolyester, at least a portion of the ethylene glycol units of which are replaced by 1,4-cyclohexanedimethanol. Similarly, U.S. Pat. No. 5,635,584 discloses reacting post-consumer or waste polyesters with glycols to produce monomers or low molecular weight oligomers by depolymerization of the polyester. The monomers or oligomers, as the case may be, are subsequently purified using one or more steps, including filtration, crystallization, and optional adsorbent treatment or evaporation. The monomers or oligomers thus produced are particularly suitable as raw materials for the production of acid-based or ester-based polyesters for packaging-grade polyester materials. Since the method includes a purification step, the specifications of the polyester material previously used do not need to be strict.

Another method of reusing waste polyester is to introduce the waste into a polymerization process. U.S. Patent No. 5,559,159 thus discloses the depolymerization and repolymerization of previously used poly(ethylene terephthalate) polyester materials and copolymers thereof, particularly post-consumer polyester materials to produce bottle grade polymers containing up to 75% previously used materials. The method involves the solubilization and depolymerization of previously used polyester materials in an esterification and/or polymerization mixture containing dimethyl terephthalate, ethylene glycol and their ester exchange products. U.S. Patent No. 5,945,460 discloses a method for producing polyester articles which generates little or no polyester waste. The method provides for esterification or transesterification of one or more dicarboxylic acids or their dialkyl esters, polycondensation to produce high molecular weight polyesters, and molding or shaping of the polyester to produce the desired product. Waste generated during the molding process is recycled back to the esterification or transesterification or polycondensation portion of the method. Optionally, the waste can also be recycled to an intermediate step prior to the molding operation. U.S. Patent No. 7,297,721 discloses a method for preparing high molecular weight crystalline PET: it uses up to 50% of post-consumer recycled PET bottle flakes together with pure terephthalic acid, isophthalic acid and ethylene glycol as virgin raw material in the presence of a combination of catalysts and additives to obtain an intermediate prepolymer heel with a low degree of polymerization, further subjected to autoclaving to produce an amorphous melt, followed by solid state polymerization.

As described in more detail in U.S. Pat. No. 2,720,507, which is incorporated herein by reference, copolyesters can generally be prepared by condensing a dicarboxylic acid or a dicarboxylic acid ester with a diol in an inert atmosphere in the presence of a catalyst at elevated temperature (which is gradually increased to a temperature of up to about 225° C. to 310° C. during the condensation process) and conducting the condensation under reduced pressure in the late stage of the condensation.

In some embodiments, in the process of manufacturing the method for the copolyesters that can be used in the present disclosure, certain reagents that color the polymer, including toners or dyes, can be added to the melt. In one embodiment, a bluing toner is added to the melt to reduce the b* of the resulting copolyester polymer melt phase product. Such bluing agents include blue inorganic and organic toners and/or dyes. In addition, red toners and/or dyes can also be used to adjust the a* color. Organic toners can be used, such as blue and red organic toners, such as those described in U.S. Patent Nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entirety. Organic toners can be fed in as a premixed composition. The premixed composition can be a pure blend of red and blue compounds, or the composition can be pre-dissolved or pulped in one of the raw materials, such as ethylene glycol.

The total amount of toner components added may depend on the amount of yellow inherent in the base copolyester and the effectiveness of the toner. In one embodiment, a total organic toner component concentration of up to about 15 ppm may be used, and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of bluing additive may be 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or the polycondensation zone. It is preferred that the toner be added to the esterification zone or to the early stages of the polycondensation zone, such as in a prepolymer reactor.

In one aspect of the present disclosure, the copolyester composition further comprises recycled polyethylene terephthalate (rPET) or recycled polyester. It is desirable to incorporate recycled PET (rPET) or recycled polyester into new molded or extruded articles. The use of rPET or recycled polyester reduces the environmental footprint of product supply and improves overall life cycle analysis. The use of rPET or recycled polyester provides economic advantages and will reduce the total amount of packaging-related products sent to landfills or that may end up polluting the ocean or other bodies of water.

There is no limitation on the recycled polyethylene terephthalate (rPET) or recycled polyester that can be used to make blends with the copolyester compositions of the present disclosure. In one embodiment, the rPET or recycled polyester is mechanically recycled. In one embodiment, the rPETrPET or recycled polyester is made from chemically recycled monomers (made by any known depolymerization process).

In one embodiment, the rPET may have slight modifications, such as with up to 5 mol % of isophthalic acid and/or up to 5 mol % of CHDM or other diols. In one embodiment, the recycled PET (rPET) can be almost any "waste" industrial or post-consumer PET. In one embodiment, the rPET that can be used in the blend composition of the present disclosure can be post-consumer recycled PET. In one embodiment, the rPET is post-industrial recycled PET. In one embodiment, the rPET is post-consumer PET from soft drink bottles. In one embodiment, waste PET fibers, waste PET films, and low-quality PET polymers are also suitable sources of rPET. In one embodiment, recycled PET essentially comprises PET, although other copolyesters may also be used, especially when they have a similar structure to PET, such as PET copolymers, etc. In one embodiment, the rPET is clean. In one embodiment, the rPET is essentially free of contaminants. In one embodiment, the rPET can be in the form of bottle flakes.

In one embodiment, the copolyester composition comprises 0 to 50 wt% rPET. In one embodiment, the copolyester composition comprises 1 to 40 wt% rPET. In one embodiment, the copolyester composition comprises 2 to 30 wt% rPET. In one embodiment, the copolyester composition comprises 3 to 20 wt% rPET. In one embodiment, the copolyester composition comprises 4 to 15 wt% rPET. In one embodiment, the copolyester composition comprises 5 to 10 wt% rPET.

In one embodiment, up to about 50 wt% rPET may be incorporated into the copolyester compositions of the present disclosure. In one embodiment, the rPET/copolyester blend is 15-50 wt% rPET. In one embodiment, the rPET/copolyester blend is 25-40 wt% rPET. In one embodiment, the rPET/copolyester blend is 20-30 wt% rPET. In one embodiment, the rPET/copolyester blend is 15-50 wt% rPET and 50-85 wt% of at least one copolyester.

The copolyester/rPET blend can be prepared by conventional processing techniques known in the art, such as melt blending, melt mixing, compounding by single screw extrusion, compounding by twin screw extrusion, batch melt mixing equipment, or combinations thereof. In one embodiment, the copolyester/rPET blend is compounded at a temperature of 220-320°C. In one embodiment, the copolyester/rPET blend is compounded at a temperature of 220-300°C. In one embodiment, the copolyester/rPET blend may be predried at 60-160°C. In one embodiment, the copolyester/rPET blend is not predried. In one embodiment, the compounding may be performed under vacuum. In one embodiment, the compounding is not performed under vacuum.

In some embodiments, the copolyester composition may also contain conventional additives in amounts required for the intended application. In some embodiments, the copolyester composition may contain 0.01 to 25 wt % or 0.01 to 10 wt % of the total composition of conventional additives such as colorants, toners, dyes, mold release agents, flame retardants, extenders, reinforcing agents or materials, fillers, antistatic agents, antimicrobial agents, antifungal agents, self-cleaning or low surface energy agents, fragrances or flavors, antioxidants, extrusion aids, slip agents, release agents, carbon black and other pigments, plasticizers, glass bubbles, nucleating agents, stabilizers, including but not limited to UV stabilizers, heat stabilizers and/or their reaction products, fillers and impact modifiers, etc., and mixtures thereof, the utility of which in copolyester blends is known in the art. Examples of commercially available impact modifiers include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core-shell impact modifiers. Residues of these additives are also contemplated as part of the copolyester composition.

Reinforcement materials can be added to compositions useful for the present disclosure. Reinforcement materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers and polymer fibers and combinations thereof. In one embodiment, the reinforcement material comprises glass, such as a mixture of fiberglass filaments, glass and talc, a mixture of glass and mica, and a mixture of glass and polymer fibers.

In one embodiment, the composition of the present disclosure can be used as plastics, films, fibers and sheets. The composition of the present disclosure can be used as molded or formed articles, molded or formed parts or solid plastic objects. In one embodiment, the composition of the present disclosure can be used as molded parts or molded articles. In one embodiment, the composition is suitable for any application requiring clear hard plastics. In one embodiment, the composition is suitable for any application requiring a reclosable lid with a living hinge. Examples of such parts and articles include cups, cans, cosmetic packaging, covers, decorative covers, personal care product packaging, electronic product housings, bottles, bottle caps, electronic equipment housings, automotive parts, automotive interiors, toys, toy parts, medical equipment, dental trays, dental appliances, dental floss packaging, containers, food containers, transport containers, packaging, insulation products, insulation containers, trays, food trays, food trays, tumblers, storage boxes, bottles, water bottles, vacuum cleaner parts, health care products, commercial catering products, boxes, machine guards, medical packaging, etc.

The present disclosure further relates to manufactured articles comprising films and/or sheets comprising the copolyester compositions described herein.In some embodiments, the films and/or sheets of the present disclosure can be any thickness desired for the intended application.

The present disclosure further relates to films and/or sheets as described herein. Methods for molding the copolyester composition into films and/or sheets include any method known in the art. Examples of films and/or sheets disclosed herein include, but are not limited to, extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, and methods for making films and/or sheets include, but are not limited to, extrusion, calendering, and compression molding.

The present disclosure further relates to molded or shaped articles as described herein. Methods of forming the copolyester composition into molded or shaped articles include any known methods in the art. Examples of molded or shaped articles of the present disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Methods of making molded articles include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. The methods of the present disclosure may include any thermoforming method known in the art. The methods of the present disclosure may include any blow molding method known in the art, including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

The present disclosure includes any injection molding manufacturing method known in the art. Although not limited thereto, a typical description of an injection molding manufacturing method includes: 1) melting a composition; 2) injecting the molten composition into an injection mold to form the desired shape of the final product; 3) cooling the molded product; and 4) ejecting the product from the mold.

The present disclosure includes any injection blow molding manufacturing method known in the art. Although not limited thereto, a typical description of an injection blow molding (IBM) manufacturing method includes: 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end; 3) moving the preform into a blow mold having a desired finished shape around the preform, and closing the blow mold around the preform; 4) blowing air into the preform to stretch and expand the preform to fill the mold; 5) cooling the molded product; and 6) ejecting the product from the mold.

The present disclosure includes any injection stretch blow molding manufacturing method known in the art. Although not limited thereto, a typical description of an injection stretch blow molding (ISBM) manufacturing method includes: 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end; 3) moving the preform into a blow mold having a desired finished shape around the preform, and closing the blow mold around the preform; 4) stretching the preform using an internal stretch rod, and blowing air into the preform to stretch and expand the preform to fill the mold; 5) cooling the molded product; and 6) ejecting the product from the mold.

The present disclosure includes any extrusion blow molding manufacturing method known in the art. Although not limited thereto, a typical description of the extrusion blow molding manufacturing method includes: 1) melting a composition in an extruder; 2) extruding the molten composition through a die to form a tube (i.e., a parison) of molten polymer; 3) locking a mold having a desired finished shape around the parison; 4) blowing air into the parison to stretch and expand the extrudate to fill the mold; 5) cooling the molded article; 6) ejecting the article from the mold; and 7) removing excess plastic (commonly referred to as flash) from the article.

In one embodiment, the molded articles and parts of the present disclosure can be any thickness required for the intended end use. In one embodiment, the thickness of the molded articles and parts of the present disclosure is less than about 3 mm. In one embodiment, the thickness of the molded articles and parts is about 0.1-2 mm. In one embodiment, the thickness of the molded articles and parts is about 0.5-2 mm. In one embodiment, the thickness of the molded articles and parts is about 0.1-1 mm. In one embodiment, the lid assembly has a thickness of about 0.5-2 mm or 0.75 to 1.5 mm. In one embodiment, the container assembly has a thickness of about 0.1 to 1 mm.

One aspect of the present disclosure relates to shrink film labels that are recyclable in PET recycling streams. In one embodiment of the present disclosure, certain combinations of diol monomers in shrink film resin compositions can be made into films that have good shrink film properties and can also be crystallized so that they do not affect the recovery of the accompanying PET bottle flakes during the recycling process. These crystallizable shrink film resins can be processed with PET bottles and eventually become components in the recyclable PET bottle flakes that leave the recycling process. It has also been found that the selection and amount of a specific combination of diol monomers are important for producing films with good shrink film properties and producing crystallizable films. The optimized polyester resin compositions of the present disclosure are amorphous but crystallizable. Therefore, they exhibit good properties in film applications including as shrink films, but they have a high strain-induced crystallization melting point, so they provide compatibility in the recycling process. The shrink film labels of the present disclosure do not have to be removed during the recycling process, and they do not affect the process.

Heat shrinkable films must meet various suitability criteria to be used in the present disclosure. The film must be strong, must shrink in a controlled manner, and must provide sufficient shrink force to hold itself to the bottle without crushing the contents. In addition, when these labels are applied to polyester containers or bottles, these polyester shrink film labels must not interfere with the recycling process of the polyester containers or bottles. The shrink films of the present disclosure are advantageous because the labels can be recycled with the bottles or containers. Thus, the entire container or bottle, including the label, can be recycled and converted into new products without incurring additional handling requirements or creating new environmental issues. Heat shrinkable films are made from a variety of raw materials to meet a range of material requirements. The present disclosure describes unique and unexpected effects measured with certain monomer combinations for shrink film resin compositions.

Polyester shrink film compositions have been used commercially as shrink film labels for food, beverages, personal care, household products, etc. Typically, these shrink films are used in conjunction with clear polyethylene terephthalate (PET) bottles or containers. The entire package (bottle plus label) is then put into the recycling process. At a typical recycling center, the PET and shrink film materials can end up together at the end of the process due to the similarity in composition and density. The PET bottle flakes need to be dried to remove residual water left in the PET through the recycling process. Typically, PET is dried at temperatures above 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming clumps with the PET bottle flakes. These clumps must be removed before further processing. These clumps reduce the yield of PET bottle flakes from the process and result in additional operating steps.

Film or sheet resin compositions of the present disclosure having certain combinations of diol monomers can be made into films or sheets with good performance properties, and these compositions can also be crystallized so that they do not affect the recycling of PET bottle flakes. These crystallizable film or sheet resins can be processed with recycled PET and ultimately become a component in the recycled PET bottle flakes leaving the recycling process. It has also been found that the selection and amount of a specific combination of diol monomers is important for producing films or sheets with good performance properties and for producing crystallizable films or sheets. In other words, the polyester compositions of the present disclosure are amorphous, but they are "crystallizable" in the sense of having a high strain-induced crystalline melting point. Therefore, they exhibit good properties in film or sheet applications, including shrink films, molding, thermoforming or formed parts and/or articles, but they also have a high strain-induced crystalline melting point, so they can be recycled with PET because when recycled PET bottle flakes are subjected to high temperature drying conditions, the crystallizable polyesters of the present disclosure do not form lumps that hinder the normal mechanical operation of flaking, drying and feeding the bottle flakes into an extruder for further processing into (recycled) polyester pellets. Similarly, the sheets of the present disclosure do not have to be removed during the recycling process and therefore do not adversely affect the recycling process. (See, for example , https://www.thebalancesmb.com/recycling-polyethylene-terephthalate-pet-2877869 ).

One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising: at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mole % of terephthalic acid residues; (ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: about 75 mole % or more of ethylene glycol residues and about 25 mole % or less of other diols, the other diols comprising one or more of: (i) from about 0.1 to less than about 24 mole % of neopentyl glycol residues; (ii) from 0 to less than about 24 mole % of 1,4-cyclohexanedimethanol residues; (iii) from about 1 to less than about 10 mole % of the total diethylene glycol residues in the final polyester composition; wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the diol component is 100 mole %.

One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising: at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mole % of terephthalic acid residues; (ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: about 80 mole % or more of ethylene glycol residues and about 20 mole % or less of other diols, the other diols comprising: (i) from about 5 to less than about 17 mole % of neopentyl glycol residues; (ii) from about 2 to less than about 10 mole % of 1,4-cyclohexanedimethanol residues; (iii) from about 1 to less than about 5 mole % of the total diethylene glycol residues in the final polyester composition; wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the diol component is 100 mole %.

One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising: at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mole % of terephthalic acid residues; (ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: about 76 mole % or more of ethylene glycol residues and about 24 mole % or less of an amorphous content selected from: (i) neopentyl glycol residues; (ii) cyclohexanedimethanol residues; and (iii) diethylene glycol residues in the final polyester composition; wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the diol component is 100 mole %.

One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising: at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mole % of terephthalic acid residues; (ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) from about 1 to about 30 mole % of neopentyl glycol residues; (ii) from about 1 to about less than 30 mole % of 1,4-cyclohexanedimethanol residues; (iii) from about 1.5 to 6 mole % of diethylene glycol residues; and wherein the remaining diol component comprises: (iv) ethylene glycol residues, and (v) 0 to 20 mole % of residues of at least one modifying diol; wherein the total mole % of the dicarboxylic acid component is 100 mole %, and wherein the total mole % of the diol component is 100 mole %.

One embodiment of the present disclosure is the crystallizable film of any of the preceding embodiments, wherein the film is stretched in at least one direction and the stretched film has a strain-induced crystalline melting point of 190°C or higher. One embodiment of the present disclosure is the crystallizable film of any of the preceding embodiments, wherein the film is stretched in at least one direction and the stretched film has a strain-induced crystalline melting point of about 190°C to about 215°C.

One embodiment of the present disclosure is an extruded or calendered film comprising the crystallizable film of any of the preceding embodiments.

One embodiment of the present disclosure is a crystallizable film comprising a blend of polyester compositions, the blend comprising: (1) at least one crystallizable polyester comprising: residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range and (2) at least one amorphous polyester comprising: residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range.

One embodiment of the present disclosure is directed to a crystallizable polyester blend composition. In one embodiment, the crystallizable polyester blend composition comprises: (a) 5 to 95 weight percent of a crystallizable polyester composition and (b) 5 to 95 weight percent of at least one amorphous polyester composition.

One embodiment of the present disclosure is a crystallizable composition comprising a blend of polyester compositions, the blend comprising:

(1) 5 to 80% of at least one crystallizable polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

The diol component is selected from (b) or (b'), wherein

(b) is a diol component comprising:

About 75 mole % or more of ethylene glycol residues and

About 25 mole % or less of other diols, the other diols comprising one or more of:

(i) from about 0 to less than about 25 mole % neopentyl glycol residues;

(ii) from about 0 to less than about 25 mole % of 1,4-cyclohexanedimethanol residues;

(iii) from about 0 to less than about 10 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and wherein

(b') is a diol component comprising:

About 75 mole % or more of ethylene glycol residues and

About 25 mole % or less of other diols, the other diols comprising one or more of:

(i) from about 0.1 to less than about 24 mole percent neopentyl glycol residues;

(ii) from about 0.1 to less than about 24 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) from about 1 to less than about 10 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %,

and

(2) 20-95% of at least one amorphous polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

About 60 mol % or more of ethylene glycol residues and

About 40 mole % or less of other diols, the other diols comprising one or more of:

(i) from about 0 to less than about 40 mole % neopentyl glycol residues;

(ii) from about 0 to less than about 40 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) from about 0 to less than about 15 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and wherein (1) and (2) are different.

One embodiment of the present disclosure is a crystallizable composition comprising a blend of polyester compositions, the blend comprising:

(1) 5 to 80% of at least one crystallizable polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

About 80 mol % or more of ethylene glycol residues and

About 20 mole % or less of other diols, the other diols comprising one or more of:

(i) from about 0 to less than about 20 mole % neopentyl glycol residues;

(ii) from about 0 to less than about 20 mole % of 1,4-cyclohexanedimethanol residues;

(iii) from about 0 to less than about 10 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and

(2) 20-95% of at least one amorphous polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

About 70 mole % or more of ethylene glycol residues and

About 30 mole % or less of other diols, the other diols comprising one or more of:

(i) from about 0 to less than about 30 mole % neopentyl glycol residues;

(ii) from about 0 to less than about 30 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) from about 0 to less than about 15 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and wherein (1) and (2) are different.

One embodiment of the present disclosure is a crystallizable composition comprising a blend of polyester compositions, the blend comprising:

(1) 5 to 80% of at least one crystallizable polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

About 85 mol % or more of ethylene glycol residues and

About 15 mol % or less of other diols, the other diols comprising one or more of:

(i) from about 0 to less than about 15 mole % neopentyl glycol residues;

(ii) from about 0 to less than about 15 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) from about 0 to less than about 5 mole percent of the total diethylene glycol residues in the final polyester composition;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and

(2) 20-95% of at least one amorphous polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

About 60 mol % or more of ethylene glycol residues and

About 40 mole % or less of other diols, the other diols comprising one or more of:

(i) neopentyl glycol residues;

(ii) 1,4-cyclohexanedimethanol residues; and

(iii) diethylene glycol residues in the final polyester composition, whether or not formed in situ;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and wherein (1) and (2) are different.

One embodiment of the present disclosure is a crystallizable composition comprising a blend of polyester compositions, the blend comprising:

(1) 5 to 80% of at least one crystallizable polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

(i) from about 0 to about 30 mole % neopentyl glycol residues;

(ii) from about 0 to about less than 30 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) diethylene glycol residues; and

The remaining diol component comprises:

(iv) ethylene glycol residues, and

(v) optionally, 0.1 to 20 mole % of the residue of at least one modifying diol;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; and

(2) 20-95% of at least one amorphous polyester comprising:

(a) a dicarboxylic acid component comprising:

(i) from about 70 to about 100 mole percent of terephthalic acid residues;

(ii) from about 0 to about 30 mole % of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(b) a diol component comprising:

(i) from about 0 to about 40 mole % neopentyl glycol residues;

(ii) from about 0 to about less than 40 mole percent of 1,4-cyclohexanedimethanol residues;

(iii) diethylene glycol residues, whether or not formed in situ; and

The remaining diol component comprises:

(iv) ethylene glycol residues, and

(v) 0 to 20 mol %, or 0 to 10 mol %, or 0 to 5 mol % of the residue of at least one modifying diol;

wherein the total mole % of the dicarboxylic acid components is 100 mole %, and wherein the total mole % of the diol components is 100 mole %; wherein (1) and (2) are different.

In other embodiments of the present disclosure, the blend composition has a crystalline melting point at about 200 to about 255°C.

In other embodiments of the present disclosure, the above blend has a crystalline melting point in the range of about 220° C. to about 230° C. or in the range of about 245° C. to about 255° C. In other embodiments, component (1) has a crystalline melting point of about 220° C. to about 230° C.

One embodiment of the present disclosure is the crystallizable film of the aforementioned embodiment, wherein the film is stretched in at least one direction and the stretched film has a strain-induced crystalline melting point of 200° C. or higher.

One embodiment of the present disclosure is a polyester recycle stream comprising recycled poly(ethylene terephthalate) bottle flakes having mixed therewith at least about 0.1 wt. % of the crystallizable recycled shrink film or thermoformed sheet of the present disclosure.

The crystallizable compositions of the present disclosure thus constitute an advantageous component of a PET recycle stream, since such compositions can accompany the PET in the recycle stream without the need for an additional separation step. Accordingly, in one embodiment of the present disclosure, there is provided a polyester recycle stream comprising recycled polyethylene terephthalate bottle flakes having at least about 0.1 wt. % of the crystallizable compositions of the present disclosure mixed therewith. In another embodiment, wherein the stream passes through "Critical Guidance Protocol for Clear PET Articles with Labels and Closures", dated April 11, 2019, File No. PET-CG-02.

Heat shrinkable plastic films are used as covers to hold objects together and as outer packaging for bottles, cans and other types of containers. For example, such films are used to cover the cap, neck, shoulder or ridge of a bottle or the entire bottle; to label, protect, wrap or add value to a product; and for other reasons. In addition, such films can be used as covers to package objects such as boxes, bottles, boards, sticks or notebooks together in groups, and such films can also be tightly attached as packaging materials. The above uses take advantage of the shrinkability and internal shrinkage stress of the film.

Heat shrinkable films must meet various suitability criteria to be used in this application. The film must be strong, must shrink in a controlled manner, and must provide sufficient shrinkage force to hold itself to the bottle without crushing the contents. In addition, when these labels are applied to polyester containers, they must not interfere with the recycling process of the PET bottles. In fact, it would be advantageous if the label were also recyclable so that the entire bottle could be recycled and converted into new products without incurring additional handling requirements or creating new environmental problems. Heat shrinkable films are made from a variety of raw materials to meet a range of material requirements. The present disclosure describes unique and unexpected effects measured with certain monomer combinations that improve the recyclability of polyester shrink film labels.

Polyester shrink film compositions are used commercially as shrink film labels for food, beverages, personal care, household products, etc. Typically, these shrink films are used in conjunction with clear polyethylene terephthalate (PET) bottles or containers. The entire package (bottle plus label) is then put into the recycling process. At a typical recycling center, the PET and shrink film materials are usually eventually combined together at the end of the process due to the similarity in composition and density. The PET bottle flakes need to be dried to remove residual water left in the PET through the recycling process. Typically, during the recycling process, PET is dried at temperatures above 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming clumps with the PET bottle flakes. These clumps must be removed before further processing. These clumps reduce the yield of PET bottle flakes from the process and result in additional operating steps.

In the present disclosure, certain combinations of diol monomers in shrink film resin compositions can produce shrink films with good performance properties that can also be crystallized so that they do not affect the recycling of PET bottle flakes during the recycling process. These crystallizable shrink film resins can be processed with PET bottles and ultimately become a component in the recycled PET bottle flakes leaving the recycling process. It has also been discovered that the selection and amount of a specific combination of diol monomers is important for producing films with good shrink film properties and films that are crystallizable.

The diol component of the polyester composition that can be used as the shrink film resin in the present disclosure may include, but is not limited to, wherein the sum of the residues of 1,4-cyclohexanedimethanol and the residues of neopentyl glycol in the final polyester composition is 1 to 30 mol%, or 1 to 25 mol%, 1 to 20 mol%, or 1 to 15 mol%, or 1 to 10 mol%, or 2 to 30 mol%, or 2 to 25 mol%, or 2 to 20 mol%, or 2 to 15 mol%, or 2 to 10 mol%, or 3 to 30 mol%, or 3 to 25 mol%, or 3 to 20 mol%, or 3 to 15 mol%, or 3 to 10 mol%, 4 to 30 mol%, or 4 to 25 mol%, 4 to 20 mol%, or %, 4 to 15 mol%, or 4 to 10 mol%, 5 to 30 mol%, or 5 to 25 mol%, 5 to 20 mol%, or 5 to 15 mol%, or 5 to 10 mol%, 6 to 30 mol%, or 6 to 25 mol%, 6 to 20 mol%, or 6 to 15 mol%, or 6 to 10 mol%, 7 to 30 mol%, or 7 to 25 mol%, 7 to 20 mol%, or 7 to 15 mol%, or 7 to 10 mol%, 8 to 30 mol%, or 8 to 25 mol%, 8 to 20 mol%, or 8 to 15 mol%, or 8 to 10 mol%, 9 to 30 mol%, or 9 to 25 mol%, 9 to 20 mol%, or 9 to 15 mol%, or 9 to 10 % by mole, 10 to 30 % by mole, or 10 to 25 % by mole, 10 to 20 % by mole, or 10 to 15 % by mole, or 11 to 30 % by mole, or 11 to 30 % by mole, or 11 to 25 % by mole, 11 to 20 % by mole, or 11 to 15 % by mole, or 12 to 30 % by mole, 12 to 25 % by mole, or 12 to 20 % by mole, 12 to 15 % by mole, or 13 to 30 % by mole, or 13 to 25 % by mole, 13 to 20 % by mole, or 13 to 15 % by mole, 14 to 30 % by mole, or 14 to 25 % by mole, or 14 to 20 % by mole, 14 to 15 % by mole, or 15 to 30 % by mole, 15 to 25 % by mole, or 15 to %, or 11 to 29 mol%, or 12 to 29 mol%, or 13 to 29 mol%, or 14 to 29 mol%, or 15 to 29 mol%, or 10 to 28 mol%, or 11 to 28 mol%, or 12 to 28 mol%, or 13 to 28 mol%, or 14 to 28 mol%, or 15 to 28 mol% of the composition. In one embodiment, the sum of the residues of 1,4-cyclohexanedimethanol and the residues of neopentyl glycol in the final polyester composition may be 1 to 16 mol%, 2 to 14 mol%, 4 to 15 mol%, or 2 to 21 mol%, or 2 to less than 20 mol%, or 4 to 20 mol%, or 5 to 18 mol%, or 10 to 21 mol%, or 12 to 21 mol%, wherein the total mol% of the diol components is 100 mol%.

In one embodiment, the diol component of the polyester composition that can be used as the shrink film resin in the present disclosure may contain 1 to 30 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 1 to 25 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 1 to 17 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 5 to 20 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 10 to 20 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component useful for the polyester composition of the present disclosure may contain 10 to 15 mol% of neopentyl glycol based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component useful for the polyester composition of the present disclosure may contain 15 to 25 mol% of neopentyl glycol residues based on the total mol% of the diol component being 100 mol%.

In one embodiment, the diol component of the polyester composition useful as the shrink film resin in the present disclosure may contain 0.01 to 30 mol%, or 0.1 to 20 mol%, or 2 to 20 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 10 mol%, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.0 1 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, 3 to 15 mol%, or 3 to 14 mol%, or 3 to 13 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 5 mol%, or 1 to 7 mol%, or 1 to 5 mol%, or 1 to 3 mol% of 1,4-cyclohexanedimethanol residues.

In one embodiment, the diol component of the polyester composition that can be used as the shrink film resin in the present disclosure may contain 0.01 to 15 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component as 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 0 to less than 15 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component as 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 0.01 to 10 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component as 100 mol%. In one embodiment, the diol component that can be used for the polyester composition of the present disclosure may contain 0 to less than 10 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component as 100 mol%. In one embodiment, the diol component useful for the polyester composition of the present disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component being 100 mol%. In one embodiment, the diol component useful for the polyester composition of the present disclosure may contain 0 to less than 5 mol% of 1,4-cyclohexanedimethanol residues based on the total mol% of the diol component being 100 mol%.

It should be understood that some other diol residues may be formed in situ during processing. In one embodiment, the diol component of the polyester composition that can be used as a shrink film resin as described in the present disclosure may contain any amount of diethylene glycol residues that are formed in situ during processing and/or intentionally added. For example, in one embodiment, the polyester composition that can be used in the present disclosure may contain 1 to 15 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 4 to 12 mol%, or 4 to 11 mol%, or 4 to 10 mol%, or 4 to 9 mol%, or 5 to 12 mol%, or 5 to 11 mol%, or 5 to 10 mol%, or 5 to 9 mol% of diethylene glycol residues based on the total mole % of the diol component as 100 mol%.

In one embodiment, the total amount of diethylene glycol residues present in the polyester composition useful as the shrink film resin in the present disclosure, whether formed in situ during processing or intentionally added, or both, can be 4 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol% of diethylene glycol residues, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 6 mol%, or 2 to 5 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol%, based on the total mol% of the diol component being 100 mol%, or in some embodiments, there are no intentionally added diethylene glycol residues.

For all embodiments of the polyester composition useful as the shrink film resin in the present disclosure, the remaining diol component may contain any amount of ethylene glycol residues based on the total mole % of the diol component being 100 mole %. In one embodiment, the polyester portion of the polyester composition useful in the present disclosure may contain 50 mole % or more, or 55 mole % or more, or 60 mole % or more, or 65 mole % or more, or 70 mole % or more, or 75 mole % or more, or 80 mole % or more, or 85 mole % or more, or 90 mole % or more, or 95 mole % or more, or 50 to 85 mole %, or 50 to 80 mole %, or 55 to 80 mole %, or 60 to 80 mole %, or 50 to 75 mole %, or 55 to 75 mole %, or 60 to 75 mole %, or 65 to 75 mole %, or 70 to 80 mole %, or 75 to 85 mole % of ethylene glycol residues based on the total mole % of the diol component being 100 mole %.

In one embodiment, the diol component of the polyester composition useful as the shrink film resin in the present disclosure may contain up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, or up to 16 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol% or less of one or more modifying diols (modifying diols are defined as diols that are not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In certain embodiments, the polyester composition useful in the present disclosure may contain 10 mol% or less of one or more modifying diols. In certain embodiments, polyesters useful in the present disclosure may contain 5 mol % or less of one or more modified diols. In certain embodiments, polyesters useful in the present disclosure may contain 3 mol % or less of one or more modified diols. In another embodiment, polyesters useful in the present disclosure may contain 0 mol % of modified diols. However, it is expected that some other diol residues may be formed in situ so that residual amounts formed in situ are also an embodiment of the present disclosure.

In an embodiment, if used, the modified glycol used in the polyester composition that can be used as a shrink film resin as defined herein contains 2 to 16 carbon atoms. Examples of modified glycols include, but are not limited to, 1,2-propylene glycol, 1,3-propylene glycol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and mixtures thereof. In one embodiment, isosorbide is a modified glycol. In another embodiment, the modified glycol includes, but is not limited to, at least one of 1,3-propylene glycol and 1,4-butanediol. In one embodiment, 1,3-propylene glycol and/or 1,4-butanediol can be excluded. If 1,4- or 1,3-butanediol is used, greater than 4 mol % or greater than 5 mol % can be provided in one embodiment. In one embodiment, the at least one modifying diol is 1,4-butanediol present in an amount of 5 to 25 mole %.In certain embodiments, the polyester composition contains no added modifying diol.

In one embodiment, a shrink film is provided, comprising a polyester composition, the polyester composition further comprising: 1,4-cyclohexanedimethanol residues present in an amount of 0.01 to about 10 mol %, diethylene glycol residues present in an amount of 2 to 9 mol %, neopentyl glycol residues present in an amount of 5 to 30 mol %, and ethylene glycol residues present in an amount of 60 mol % or more, based on the total mol % of the diol component being 100 mol %.

In one embodiment, the polyester composition useful as the shrink film resin in the present disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides, including, for example, epoxidized novolac resins and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during a conversion process, such as injection molding or extrusion.

In certain embodiments, the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired, but is typically from about 0.1 wt % to about 10 wt %, such as from about 0.1 to about 5 wt %, based on the total weight of the polyester.

Unless otherwise specified, it is contemplated that the polyester compositions useful as shrink film resins in the present disclosure may have at least one intrinsic viscosity range described herein and at least one monomer range for the polyester compositions described herein. It is also contemplated that the polyester compositions useful in the present disclosure may have at least one Tg range described herein and at least one monomer range for the polyester compositions described herein, unless otherwise specified. It is also contemplated that the polyester compositions useful in the present disclosure may have at least one intrinsic viscosity range described herein, at least one Tg range described herein, and at least one monomer range for the polyester compositions described herein, unless otherwise specified.

For embodiments of the present disclosure, the polyester composition useful as the shrink film resin in the present disclosure may exhibit at least one of the following intrinsic viscosities measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/dL at 25° C.: 0.50 to 1.2 dL/g; 0.50 to 1.0 dL/g; 0.50 to 0.90 dL/g; 0.50 to 0.80 dL/g; 0.55 to 0.80 dL/g; 0.60 to 0.80 dL/g; 0.65 to 0.80 dL/g; 0.70 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.55 to 0.75 dL/g; or 0.60 to 0.75 dL/g.

The glass transition temperature and strain-induced crystalline melting point (Tg and Tm, respectively) of the polyester compositions useful as shrink film resins in the present disclosure were determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C/min. Tm was measured on the first heating of the stretched sample and Tg was measured during the second heating step. Additionally, the samples were crystallized in a forced air oven at 170°C for 2 hours and then analyzed by DSC. For all samples, there was generally no crystalline melting point during the second heating of the DSC scan at a heating rate of 20°C/min.

In certain embodiments, the oriented film, shrink film, or thermoformed sheet of the present disclosure comprises a polyester/polyester composition, wherein the polyester has a Tg of 60 to 80° C.; 70 to 80° C.; 65 to 80° C.; 72 to 77° C., or 65 to 75° C. In certain embodiments, the intrinsic viscosity of the polyester is 0.68 to 0.75 dL/g as measured at a concentration of 0.5 g/dL in 60/40 (wt/wt) phenol/tetrachloroethane at 25° C., and the polyester has a Tg of 72° C. to 77° C. as measured using a TA DSC2920 from Thermal Analyst Instrument at a scan rate of 20° C./min.

In certain embodiments, these Tg ranges can be met with or without the addition of at least one plasticizer during the polymerization process or during the extrusion process or during the compounding process.

In embodiments of the present disclosure, certain oriented films and/or shrinkable films comprising polyesters and/or polyester compositions useful in the present disclosure may have a unique combination of all of the following properties: good stretchability, controlled shrinkage properties, certain toughness, certain intrinsic viscosity, certain glass transition temperature (Tg), certain strain induced crystalline melting point, certain flexural modulus, certain density, certain tensile modulus, certain surface tension, good melt viscosity, good clarity, and good color. In certain embodiments, the oriented films and/or shrinkable films may be used as roll-fed or conventional shrink sleeve labels, may be easily printed, and joined by conventional means. The oriented films and/or shrinkable films of the present disclosure may be prepared using any procedure known to those skilled in the art.

In one embodiment, certain polyester compositions useful as shrink film resins in the present disclosure may be visually clear. The term "visually clear" is defined herein as the apparent absence of cloudiness, haziness, and/or muddiness upon visual inspection.

The polyester portion of the polyester composition useful as the shrink film resin in the present disclosure can be made by methods known in the literature, such as by a process in a homogeneous solution, by a transesterification process in a melt, and by a two-phase interface process. Suitable methods include, but are not limited to, a step of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100° C. to 315° C. and a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. For methods of producing polyesters, see U.S. Pat. No. 3,772,405, the disclosure of which is incorporated herein by reference for such methods.

In certain embodiments, the polyesters can be prepared by condensing a dicarboxylic acid or a dicarboxylic acid ester with a diol in an inert atmosphere in the presence of a catalyst at gradually increasing temperatures during the condensation and at a reduced pressure in the late stages of the condensation, as described in more detail in U.S. Pat. No. 2,720,507, which is incorporated herein by reference.

In some embodiments, in the process of making the polyester that can be used for the present disclosure, certain reagents that color the polymer, including toners or dyes, can be added to the melt. In one embodiment, a bluing toner is added to the melt to reduce the b* of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toners and/or dyes. In addition, red toners and/or dyes can also be used to adjust the a* color. Organic toners can be used, such as blue and red organic toners, such as those described in U.S. Patent Nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entirety. Organic toners can be fed as a premixed composition. The premixed composition can be a pure blend of red and blue compounds, or the composition can be pre-dissolved or pulped in one of the raw materials of the polyester, such as ethylene glycol.

The total amount of toner components added may depend on the amount of yellow inherent in the base polyester and the effectiveness of the toner. In one embodiment, a total organic toner component concentration of up to about 15 ppm may be used, and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of bluing additive may be 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or the polycondensation zone. Preferably, the toner is added to the esterification zone or to the early stage of the polycondensation zone, such as a prepolymer reactor.

In embodiments, the polyester composition may also contain from 0.01 to 25% by weight of the total composition of commonly used additives such as slip agents, antiblocking agents, mold release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers, including but not limited to UV stabilizers, heat stabilizers and/or reaction products thereof, fillers and impact modifiers. Examples of commercially available impact modifiers include but are not limited to ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core-shell impact modifiers. Residues of these additives are also expected to be part of the polyester composition.

In one embodiment, films and shrink films according to the present disclosure may contain 0.01 to 10 weight percent of a polyester plasticizer, such as those described in U.S. Pat. No. 10,329,393, which is incorporated herein by reference. In one embodiment, the shrink film may contain 0.01 to 10 weight percent of a polyester plasticizer compounded in the copolyester of the present invention.

In one aspect, the present disclosure relates to shrink films, extruded sheets, thermoformed articles and molded articles comprising the polyester compositions of the present disclosure. Methods of molding the polyester compositions into films and/or sheets are well known in the art. Examples of sheets that can be used in the present disclosure include, but are not limited to, extruded sheets, compression molded films, calendered films and/or sheets, solution cast films and/or sheets. In one aspect, methods of making films and/or sheets that can be used to produce shrink films of the present disclosure include, but are not limited to, extrusion, compression molding, calendering and solution casting.

In one embodiment, the polyester composition useful as the shrink film resin in the present disclosure is made into a film using any method known in the art for producing films from polyesters, such as solution casting, extrusion, compression molding, or calendaring (see, for example, U.S. Pat. Nos. 6,846,440; 6,551,699; 6,551,688; and 6,068,910, which are incorporated herein by reference).

In one embodiment, the formed film is subsequently oriented in one or more directions (e.g., a uniaxial and/or biaxially oriented film). Such orientation of the film can be performed by any method known in the art using standard orientation conditions. For example, the oriented film of the present disclosure can be made of a film having a thickness of about 100 to 400 microns, such as an extruded, cast, or calendered film, which can be oriented at a ratio of 5:1 to 3:1 at a temperature of Tg to Tg+55°C or 70°C to 125°C, for example, at a ratio of 5:1 or 3:1 at a temperature of 70°C to 100°C, and can be oriented to a thickness of 20 to 80 microns. In one embodiment, the orientation of the initial pre-shrink film can be performed on a tenter frame according to these orientation conditions.

The shrink film of the present disclosure may have a shrinkage initiation temperature of about 55° C. to about 80° C., or about 55° C. to about 75° C., or about 55° C. to about 70° C. The shrinkage initiation temperature is the temperature at which shrinkage begins to occur.

In certain embodiments, the polyester compositions useful in the present disclosure may have a density of 1.6 g/cc or less, or 1.5 g/cc or less, or 1.4 g/cc or less, or 1.1 g/cc to 1.5 g/cc, or 1.2 g/cc to 1.4 g/cc, or 1.2 g/cc to 1.35 g/cc.

In one embodiment, the density of the film is reduced by introducing many small voids or pores into the film or shaped article. This method is called "voiding", which may also be referred to as "cavitating" or "microvoiding". The voids are obtained by incorporating about 1 to about 50% by weight of small organic or inorganic particles (including glass microspheres) or "inclusions" (referred to in the art as "pore-forming" or "cavitating" agents) into a matrix polymer and stretching the polymer in at least one direction to orient the polymer. During the stretching process, small holes or voids are formed around the pore-forming agent. When voids are introduced into the polymer film, the resulting void-containing film not only has a lower density than a void-free film, but also becomes opaque and forms a paper-like surface. This surface also has the advantage of improved printability; that is, the surface is able to accept many inks at a significantly higher capacity than a void-free film. Typical examples of void-containing films are described in U.S. Patent Nos. 3,426,754; 3,944,699; 4,138,459; 4,582,752; 4,632,869; 4,770,931; 5,176,954; 5,435,955; 5,843,578; 6,004,664; 6,287,680; 6,500,533; 6,720,085; U.S. Patent Application Publication Nos. 2001/0036545; 2003/0068453; 2003/0165671; 2003/0170427; Japanese Patent Application No. 61-037827; 63-193822; 2004-181863; European Patent No. 0581970B1 and European Patent Application No. 0214859A2.

In certain embodiments, the extruded film is oriented while being stretched.Oriented films or shrinkable films of the present disclosure can be made of films with any thickness, depending on the desired end use.In one embodiment, the ideal condition is that the oriented film and/or shrinkable film can be printed with ink for use in applications including labels, photographic films that can be attached to substrates such as paper, and/or can be used for shrinking to surround other applications outside of bottles or containers.It is desirable that polyesters that can be used for the present disclosure and another polymer, such as PET coextrusion, can be used to make films that can be used to make oriented films and/or shrink films of the present disclosure.An advantage of the latter approach is that a bonding layer may not be required in some embodiments.

In one embodiment, the uniaxial and biaxially oriented films of the present disclosure may be made from films having a thickness of about 100 to 400 microns, such as extruded, cast or calendered films, which may be stretched at a ratio of 6.5:1 to 3:1 at a temperature of the film's Tg to Tg+55°C and may be stretched to a thickness of 20 to 80 microns. In one embodiment, the orientation of the initial extruded film may be performed on a tenter according to these orientation conditions. The shrink film of the present disclosure may be made from the oriented film of the present disclosure.

In certain embodiments, the shrink films of the present disclosure shrink gradually with little to no wrinkling. In certain embodiments, the shrink films of the present disclosure have a transverse direction shrinkage of no greater than 40% per 5°C temperature increment.

In certain embodiments of the present disclosure, when immersed in 65°C water for 10 seconds, the shrink film of the present disclosure has a longitudinal shrinkage of 10% or less, or 5% or less, or 3% or less, or 2% or less, or no shrinkage. In certain embodiments of the present disclosure, when immersed in 65°C water for 10 seconds, the shrink film of the present disclosure has a longitudinal shrinkage of -10% to 10%, -5% to 5%, or -5% to 3%, or -5% to 2%, or -4% to 4%, or -3% to 4%, or -2% to 4%, or -2% to 2.5%, or -2% to 2%, or 0 to 2%, or no shrinkage. Negative longitudinal shrinkage percentages refer to longitudinal growth here. Positive longitudinal shrinkage refers to longitudinal shrinkage.

In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage rate in a main shrinking direction of 50% or more, or 60% or more, or 70% or more when immersed in 95° C. water for 10 seconds.

In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage in the main shrinkage direction in an amount of 50 to 90% and a longitudinal shrinkage of 10% or less, or -10% to 10%, when immersed in 95°C water for 10 seconds.

In one embodiment, the polyesters useful in the present disclosure are made into films using any method known in the art for producing films from polyesters, such as solution casting, extrusion, compression molding, or calendering. The extruded (or molded) film is then oriented in one or more directions (e.g., a uniaxially and/or biaxially oriented film). Such orientation of the film can be performed using standard orientation conditions by any method known in the art. For example, the uniaxially oriented film of the present disclosure can be made of a film having a thickness of about 100 to 400 microns, such as an extruded, cast, or calendered film, which can be stretched at a ratio of 6.5:1 to 3:1 at a temperature of Tg to Tg+55°C of the film, and can be stretched to a thickness of 20 to 80 microns. In one embodiment, the orientation of the initial extruded film can be performed on a tenter according to these orientation conditions.

In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a percent strain at break greater than 200% at a stretching speed of 500 mm/min in a direction perpendicular to the primary shrinking direction according to ASTM method D882.

In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a percent strain at break greater than 300% at a stretching speed of 500 mm/min in a direction perpendicular to the primary shrinking direction according to ASTM method D882.

In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a tensile stress at break (break stress) of 20 to 400 MPa; or 40 to 260 MPa; or 42 to 260 MPa as measured according to ASTM method D882.

In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a shrink force of 4 to 18 MPa, or 4 to 15 MPa, depending on the stretching conditions and the desired end use, as measured by ISO Method 14616. For example, certain labels made for plastic bottles may have a shrink force of 4 to 8 MPa, and certain labels made for glass bottles may have a shrink force of 10 to 14 MPa as measured by ISO Method 14616 using a LabThink FST-02 Thermal Shrinkage Tester and reported in MPa.

In one embodiment of the present disclosure, the polyester composition may be formed by reacting monomers in a known process for making polyesters generally referred to as reactor grade composition.

Molded articles, which may or may not consist of or contain a shrink film, may also be made from any of the polyester compositions disclosed herein and are included within the scope of the present disclosure.

In one embodiment, when having a pre-orientation thickness of about 100 to 400 microns and subsequently oriented on a tenter frame at a temperature of Tg to Tg+55°C at a ratio of 6.5:1 to 3:1 to a thickness of about 20 to about 80 microns, the shrink film of the present disclosure may have one or more of the following properties: (1) when immersed in 95°C water for 10 seconds, a shrinkage in the main shrinkage direction or transverse direction of greater than 60% (or greater than 70%), and a shrinkage in the machine direction of 10% or less (or -5% to 4%); Shrinkage; (2) a shrinkage initiation temperature of about 55°C to about 70°C; (3) a percent strain at break of greater than 200%, or 200 to 600%, or 200 to 500%, or 226 to 449%, or 250 to 455% in the transverse direction or in the longitudinal direction or in both directions at a stretching speed of 500 mm/min according to ASTM method D882; (4) a shrinkage of no more than 40% per 5°C temperature increment; and/or (5) a strain-induced crystalline melting point of greater than or equal to 200°C. Any combination or all of these properties may be present in the shrink film of the present disclosure. The shrink film of the present disclosure may have a combination of two or more of the above shrink film properties. The shrink film of the present disclosure may have a combination of three or more of the above shrink film properties. The shrink film of the present disclosure may have a combination of four or more of the above shrink film properties. In certain embodiments, properties (1)-(2) are present. In certain embodiments, properties (1)-(5) are present. In certain embodiments, properties (1)-(3), etc. are present.

The shrinkage percentages herein are based on an initially formed film having a thickness of about 20 to 80 microns that has been oriented on a tenter frame at a temperature of Tg to Tg+55° C. at a ratio of 6.5:1 to 3:1, for example, at a temperature of 70° C. to 85° C. at a ratio of 5:1. In one embodiment, the shrinkage properties of the oriented film used to make the shrink film of the present disclosure are not adjusted by annealing the film at a temperature above its orientation temperature.

The shape of the film that can be used to make the oriented film or shrink film of the present disclosure is not limited in any way. For example, it can be a flat film or a film that has been formed into a tube. The film formed into a tube can use a stitching solvent or a stitching adhesive to bond or bond the edges of the film together during the shrinking process. In order to produce the shrink film that can be used in the present disclosure, the polyester is first formed into a flat film and then "uniaxially stretched", which means that the polyester film is oriented in one direction. The film can also be "biaxially oriented", which means that the polyester film is oriented in two different directions; for example, the film is stretched in the machine direction and in a direction different from the machine direction. Usually, but not always, the two directions are substantially perpendicular. For example, in one embodiment, the two directions are the longitudinal or machine direction ("MD") of the film (the direction in which the film is produced on the film making machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). The biaxially oriented film can be sequentially oriented, simultaneously oriented, or oriented by some combination of simultaneous and sequential stretching.

The film can be oriented by any common method, such as roller stretching, long gap stretching, tenter stretching and tubular stretching. By using any of these methods, it is possible to carry out sequential biaxial stretching, simultaneous biaxial stretching, uniaxial stretching or a combination of these. For the biaxial stretching mentioned above, longitudinal and transverse stretching can be carried out simultaneously. Stretching can also be carried out first in one direction and then in the other direction to produce effective biaxial stretching. In one embodiment, the film is stretched by preheating the film to 5°C to 80°C above its glass transition temperature (Tg). In one embodiment, the film can be preheated to 5°C to 30°C above its Tg. In one embodiment, the stretching rate is 0.5 to 20 inches (1.27 to 50.8 cm)/second. Then, the film can be oriented, for example, in the longitudinal, transverse or two directions, 2 to 6 times the original measured value. The film can be oriented as a single-layer film, or it can be coextruded with another polyester, such as PET (polyethylene terephthalate) as a multilayer film, and then oriented.

In one embodiment, the present disclosure includes a manufactured or shaped article comprising a shrink film of any shrink film embodiment of the present disclosure. In another embodiment, the present disclosure includes a manufactured or shaped article comprising an oriented film of any oriented film embodiment of the present disclosure.

In certain embodiments, the present disclosure includes, but is not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging, battery packs, hot-fill containers, and/or industrial articles, or other applications. In one embodiment, the present disclosure includes, but is not limited to, oriented films applied to containers, packaging, plastic bottles, glass bottles, photo substrates such as paper, battery packs, hot-fill containers, and/or industrial articles, or other applications.

In certain embodiments of the present disclosure, the shrink film of the present disclosure can be formed into a label or sleeve. The label or sleeve can then be applied to a finished product, such as a container wall, a battery pack, or applied to a sheet or film.

The oriented films or shrink films of the present disclosure can be applied to shaped articles, such as containers, tubes or bottles, and are commonly used in various packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrenes, poly(vinyl chloride), polyesters, polylactic acid (PLA) are often used to make shrink labels for plastic beverage or food containers. For example, the shrink films of the present disclosure can be used in many packaging applications, wherein the shrink films applied to the shaped articles exhibit properties such as good printability, good shrinkage, good texture, high shrinkage, controlled shrinkage, good stiffness and recyclability.

Improved shrink properties and recyclability provide new business options including, but not limited to, shrink films for containers, plastic bottles, glass bottles, packaging, battery packs, hot fill containers and/or industrial articles or other applications.

The following examples further illustrate how the copolyester compositions of the present disclosure can be made into recyclable articles and evaluated, and they are intended to be exemplary only and not intended to limit the scope thereof. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C (Celsius) or at room temperature, and pressures are at or near atmospheric pressure.

Example

The present disclosure may be further illustrated by the following examples of preferred embodiments thereof, but it is to be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the present disclosure unless expressly specified otherwise.

In one embodiment of the present disclosure, the maximum fill length of the mold can be predicted based on the average thickness of the caps to be produced. For example, if the average thickness of the caps is 0.3 mm, the maximum fill length predicted based on a length/thickness ratio (l/t ratio) of 150 is 45 mm, while the maximum fill length predicted based on an l/t ratio of 100 is 30 mm.

Injection Molding Prediction

In one embodiment, it was surprisingly found that at certain lower CHDM contents, the strength value or the number of cycles before the living hinge failed increased. The strength value was measured by manually bending the living hinge of a reclosable lid. The hinge was bent by fully opening the lid to 180 degrees and folding the hinge until the lid was at the closing point (but it did not snap shut). The bending of the living hinge was continued manually until the hinge failed. One cycle is one rotation of the fully opened and closed lid. At some higher CHDM contents (e.g., 75 mol % CHDM), the living hinge failed after only a few cycles. However, at some lower CHDM contents, the living hinge did not fail even after more than 3000 cycles (note that some samples ended the test before reaching the failure point). The polyester compositions evaluated in these tests were samples of CHDM-modified PET compositions. In one embodiment, a suitable living hinge has a strength value of at least 500 cycles.

Claims (20)

1. A method of producing a recyclable lid comprising

A) Injecting at least one molten polyester into the mold using one or more injection points to produce a reclosable lid having a living hinge, wherein the average polyester flow length divided by the average thickness of the lid is less than 200;

wherein at least one polyester comprises:

(a) A dicarboxylic acid component comprising:

i) 88 to 100 mole% of terephthalic acid residues;

ii) 0 to 12 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(B) A glycol component comprising:

i) 0 to 12 mole% of 2, 4-tetramethyl-1, 3-cyclobutanediol residues;

ii) 0 to 12 mole% 1, 4-cyclohexanedimethanol residues;

iii) 0 to 12 mole% neopentyl glycol residues;

iv) 0 to 12 mole% DEG;

v) 0 to 12 mole% TMCD;

vi) 0 to 12 mole% MPDiol;

vii) 0 to 12 mole% of other modified diol residues;

viii) up to 100 mole% ethylene glycol residues;

Wherein the total mole% of the dicarboxylic acid component is 100 mole% and the total mole% of the diol component is 100 mole%; and

Wherein the polyester has a total comonomer content from glycol and acid other than Ethylene Glycol (EG), terephthalic acid (TPA), or dimethyl terephthalate (DMT), or any combination thereof, of 0 to 12 weight percent, which must be less than 12 weight percent;

wherein the intrinsic viscosity of the polyester, measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5g/100ml at 25 ℃, is from 0.60 to 1.1dL/g;

wherein the polyester has a Tg of 70 to 115 ℃;

Wherein the cap has a melting temperature (T _m) of 225-255 ℃.

2. A method of producing a recyclable lid comprising

A) Injecting at least one molten polyester into the mold using one or more injection points to produce a reclosable lid having a living hinge, wherein the average polyester flow length divided by the average thickness of the lid is less than 200;

wherein at least one polyester comprises:

(a) A dicarboxylic acid component comprising:

(i) 88 to 100 mole% of terephthalic acid residues;

(ii) 0 to 12 mole% of aromatic and/or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

(B) A glycol component comprising:

(i) 88 to 100 mole% of ethylene glycol residues; and

(Ii) 0 to 12 mole% of 1, 4-cyclohexanedimethanol residues;

Wherein the total mole% of acid residues is 100 mole% and the total mole% of glycol residues is 100 mole%;

Wherein the intrinsic viscosity (IhV) of the polyester, measured in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.25g/50ml at 25 ℃, is from 0.60 to 1.1dL/g; and

Wherein the polyester has a melting point temperature (T _m) of 225 to 255 ℃ as determined by ASTM D3418 at a scan rate of 10 ℃/min.

3. The method of claim 1 or 2, wherein the average polyester flow length divided by the average thickness of the cap is less than 175; or wherein the average polyester flow length divided by the average thickness of the cap is less than 150, or wherein the average polyester flow length divided by the average thickness of the cap is less than 100.

4. The method of claim 1 or 2, wherein the mold has one injection point.

5. The method of claim 1 or 2, wherein the mold has two injection points.

6. The method according to claim 1 or 2, wherein the cover is substantially transparent, transparent and/or clear.

7. The method of claim 1 or 2, wherein the cover is recyclable in a PET recycle stream.

8. A method according to claim 1 or 2, wherein the cover has an average thickness of 0.5-2 mm.

9. The method of claim 1 or 2, wherein the living hinge has an average thickness of 0.1-1 mm.

10. The method of claim 1 or 2, wherein the width of the living hinge is 20-80% of the length of the lid.

11. The process of claim 1, wherein the polyester has 0 to 10 mole% 1, 4-cyclohexanedimethanol residues.

12. The process of claim 1 or 2, wherein the polyester has 0 to 5 mole% 1, 4-cyclohexanedimethanol residues.

13. The process of claim 1 or 2, wherein the polyester has 0.1 to 10 mole% 1, 4-cyclohexanedimethanol residues.

14. The process of claim 1 or 2, wherein the component a-polyester has 8 to 12 mole% isophthalic acid residues.

15. The method of claim 1 or 2, wherein the living hinge has an intensity value of at least 500 cycles; or having an intensity value of at least 600 cycles; or have an intensity value of at least 1000 cycles.

16. The process of claim 1 or 2, wherein the intrinsic viscosity (IhV) of the polyester is from 0.60 to 0.8dL/g.

17. The process of claim 1 or 2, further comprising at least one polyester having a recycle content.

18. The method of claim 1or 2, wherein the EG is rEG; or wherein the DEG is rDEG or the DEG is made of rEG.

19. The method of claim 1 or 2, wherein the CHDM is rCHDM or a CHDM made from rDMT.

20. The method according to claim 1 or 2.